JP7475638B2 - Optically active compound and its manufacturing method, coordination compound, cyclic compound, and intermediate compound containing optically active compound - Google Patents

Description

The present invention relates to optically active compounds and methods for producing the same, coordination compounds containing optically active compounds, and cyclic compounds (precursor compounds) and intermediate compounds useful for obtaining optically active compounds.

Optically active compounds are used in a variety of fields, including asymmetric reactions, asymmetric catalytic reactions, pharmaceuticals, packing materials for chiral column chromatography, liquid crystal displays, and lens filters.

Optically active compounds include those that have, for example, central chirality, axial chirality, planar chirality, or asymmetry due to a helical structure. In addition, enantiomers have been reported that have a structure in which multiple rings overlap each other.

Non-Patent Document 1 proposes the total synthesis of a molecule with a Möbius strip structure.

Non-patent documents 2 and 3 propose chiral cyclic compounds having a repeating structure of phenyleneacetylene units.

Non-Patent Document 4 describes topological isomers such as [2]-catenane and doubly interlocked [2]-catenane, copper complexes having chiral knots or their ligands, etc.

J. Am. Chem. Soc., 1982, 104, pp.3219-3221 Chem. Commun., 2018, 54, pp.735-738 Chem.Sci., 2019, 10, 4782-4791 Chemical Reviews, 1995, Vol.95, No.8, “Interlocked and Intertwined Structures and Superstructures”, p.2727, p.2767

Optically active compounds with multiple ring structures are expected to selectively interact with other compounds, metals, or ions due to their special three-dimensional structure. Therefore, there is a demand for the development of optically active compounds with multiple ring structures.

A first aspect of the present invention is a method for manufacturing a semiconductor device comprising: a first base portion; a second base portion; and a plurality of cross-linking chains connecting the first base portion and the second base portion;
the plurality of crosslinked chains include at least three of a first crosslinked chain, a second crosslinked chain, and a third crosslinked chain;
one end of each of the first crosslinking chain, the second crosslinking chain, and the third crosslinking chain is bonded to three first atoms having a valence of three or more contained in the first base portion;
the other ends of the first crosslinking chain, the second crosslinking chain and the third crosslinking chain are bonded to three second atoms having a valence of three or more contained in the second base portion;
The present invention relates to an optically active compound in which the first crosslinked chain and the second crosslinked chain are overlapped so as to cross each other, thereby generating an asymmetric field.

A second aspect of the present invention is a method for manufacturing a semiconductor device comprising: a first base portion; a second base portion; and two cross-linking chains connecting the first base portion and the second base portion;
the first base portion and the second base portion each include an organic ring;
Each of the two crosslinking chains contains a repeating structure of an oxyalkylene unit,
one end of each of the two crosslinking chains is bonded to two first atoms having a valence of three or more contained in the first base portion;
The other ends of the two crosslinked chains each relate to a cyclic compound bonded to two second atoms having a valence of three or more possessed by the second base portion.

A third aspect of the present invention is a polymerizable composition comprising: a first base portion; and two molecular chains bonded to the first base portion;
the first base portion includes an organic ring;
one end of each of the molecular chains is bonded to two first atoms having a valence of three or more possessed by the first base portion,
Each of the molecular chains relates to an intermediate compound that includes repeating oxyalkylene units.

A fourth aspect of the present invention is a method for producing the optically active compound, comprising the steps of:
a first crosslinking chain and a second crosslinking chain, and the first base portion and the second base portion are connected to each other by the third crosslinking chain, and the first base portion and the second base portion are not connected to each other by the other of the first crosslinking chain and the second crosslinking chain;
and a step 2A of linking the first base portion and the second base portion at the other of the first crosslinking chain and the second crosslinking chain so that the first crosslinking chain and the second crosslinking chain cross and overlap, thereby generating an asymmetric field.

A fifth aspect of the present invention is a method for producing the optically active compound, comprising the steps of:
a step 1B of preparing a second cyclic compound in which the first base portion and the second base portion are linked by both the first crosslinked chain and the second crosslinked chain, and the first base portion and the second base portion are not linked by the third crosslinked chain;
and a second step B of connecting the first base portion and the second base portion with the third crosslinking chain, thereby crossing the first crosslinking chain and the second crosslinking chain to generate an asymmetric field.

We provide optically active compounds in which an asymmetric field is formed by crossing molecular chains in a compound having multiple ring structures.

[Optically active compound]
The optically active compound according to one aspect of the present invention includes a first base portion, a second base portion, and a plurality of crosslinking chains connecting the first base portion and the second base portion. The plurality of crosslinking chains include at least three of a first crosslinking chain, a second crosslinking chain, and a third crosslinking chain. One end of each of the first crosslinking chain, the second crosslinking chain, and the third crosslinking chain is bonded to three first atoms (i.e., three different first atoms) possessed by the first base portion. The other end of each of the first crosslinking chain, the second crosslinking chain, and the third crosslinking chain is bonded to three second atoms (i.e., three different second atoms) possessed by the second base portion. Each of the first atom and the second atom has a valence of three or more. The first crosslinking chain and the second crosslinking chain overlap so as to cross each other, generating an asymmetric field.

By connecting different atoms in the first base portion and the second base portion with at least three crosslinking chains and crossing the first crosslinking chain and the second crosslinking chain, an optically active compound can be provided that has a structure in which at least two rings overlap so that parts of them cross. Since such an optically active compound contains at least two ring structures, selective interaction with other compounds, metals, ions, etc. can be obtained. This makes it possible to apply the optically active compound to a variety of uses.

Such optically active compounds can be enantiomers, as shown in the following formulas (Ia) and (Ib).

ここで、Ａ１は、第１ベース部であり、Ａ２は第２ベース部であり、Ｃ１は第１架橋鎖であり、Ｃ２は第２架橋鎖であり、およびＣ３は第３架橋鎖である。

Here, A1 is a first base portion, A2 is a second base portion, C1 is a first crosslinking chain, C2 is a second crosslinking chain, and C3 is a third crosslinking chain.

(Base part)
Each base part of the first base part and the second base part includes at least three atoms (first atoms or second atoms) having a valence of three or more connected to a crosslinking chain, and the structure is not particularly limited as long as the structure is capable of forming an asymmetric field by the intersection of the first crosslinking chain and the second crosslinking chain. Each base part may be, for example, composed of an aliphatic molecular chain, or may include an organic ring (first organic ring). From the viewpoint of easily fixing the stereochemical configuration of the crosslinking chain and easily forming a stable asymmetric field, it is preferable that at least one of the first base part and the second base part includes a first organic ring.

The first and second atoms refer to atoms contained in each base portion that have a valence of three or more and are bonded to a crosslinking chain. There are no particular limitations on the first and second atoms as long as they have a valence of three or more, but they are preferably nonmetallic elements. Each first atom is a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, or a boron atom. Similarly, each second atom is a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, or a boron atom. From the viewpoint of easily obtaining a stable structure, it is preferable that at least two of the three first atoms are carbon atoms. Similarly, it is preferable that at least two of the three second atoms are carbon atoms.

Examples of aliphatic compounds corresponding to aliphatic molecular chains include aliphatic hydrocarbons, chain-shaped aliphatic compounds containing a heteroatom (first heteroatom) having a valence of three or more, and chain-shaped aliphatic compounds containing a heteroatom other than the first heteroatom (second heteroatom (more specifically, a heteroatom having a valence of two)). The first heteroatom can be a first atom or a second atom. Each base portion may contain one or more first heteroatoms other than the first atom or the second atom. A chain-shaped aliphatic compound containing a first heteroatom may be referred to as a first heteroatom-containing compound, and a chain-shaped aliphatic compound containing a second heteroatom may be referred to as a second heteroatom-containing compound. Aliphatic compounds also include those having a substituent (first substituent). The aliphatic compound may be either linear or branched. The aliphatic compound may be saturated or may have one or more carbon-carbon unsaturated bonds.

The number of carbon atoms in the aliphatic hydrocarbon may be 3 or more, and may be 4 or more. There is no particular upper limit to the number of carbon atoms in the aliphatic hydrocarbon, but it may be, for example, 26 or less, 18 or less, 12 or less, 10 or less, or 6 or less. These lower and upper limits may be combined in any combination.

Examples of aliphatic hydrocarbons include alkanes, alkenes, alkadienes, and alkatrienes. Specific examples of aliphatic hydrocarbons include propane, 2,2-dimethylpropane, n-butane, isobutane, butene, 2-methylbutane, n-pentane, pentene, 1,3-pentadiene, hexane, hexene, 2-ethylhexane, octane, octene, decane, and decene. However, these are merely examples, and aliphatic hydrocarbons are not limited to these specific examples.

The first heteroatom is, for example, N, P, Si, or B (especially N). The first heteroatom-containing compound may have one first heteroatom, or may have two or more first heteroatoms. When the first heteroatom-containing compound has two or more first heteroatoms, at least two of the first heteroatoms may be the same, or all of the first heteroatoms may be different.

The first heteroatom-containing compound may further have a second heteroatom. Examples of the second heteroatom include O, S, and Se. The first heteroatom-containing compound may have one second heteroatom, or may have two or more second heteroatoms. When the first heteroatom-containing compound has two or more second heteroatoms, at least two of the second heteroatoms may be the same, or all of the second heteroatoms may be different.

The number of carbon atoms in the first heteroatom-containing compound is, for example, 2 or more, and may be 3 or more, or 4 or more. The upper limit of the number of carbon atoms in the first heteroatom-containing compound is not particularly limited, but may be, for example, 26 or less, 18 or less, or 12 or less, or 10 or less, or 6 or less. These lower and upper limits can be combined in any combination.

Examples of the first heteroatom-containing compound include nitrogen-containing compounds (dialkylamines, alkylenediamines, polyalkylenepolyamines, di(alkoxyalkyl)amines, etc.), nitrogen-containing compounds in which at least some of the nitrogen atoms are replaced by P or B, compounds in which some of the carbon atoms in these compounds are replaced by Si, and compounds in which some of the carbon atoms in the aliphatic hydrocarbons listed above are replaced by Si.

Specific examples of dialkylamines include dimethylamine, diethylamine, and ethylbutylamine. Examples of alkylene polyamines include alkylene diamines, dialkylene triamines, and trialkylene tetramines. Specific examples of alkylene polyamines include ethylene diamine, diethylene triamine, and triethylene tetramine. Specific examples of di(alkoxyalkyl)amines include di(methoxyethyl)amine and di(ethoxyethyl)amine. However, these are merely examples, and the first heteroatom-containing compound is not limited to these specific examples.

The second heteroatom-containing compound may have one second heteroatom or may have two or more second heteroatoms. When the second heteroatom-containing compound has two or more second heteroatoms, at least two of the second heteroatoms may be the same, or all of the second heteroatoms may be different.

The number of carbon atoms in the second heteroatom-containing compound can be selected from the ranges described for the first heteroatom-containing compound.

Examples of the second heteroatom-containing compound include oxygen-containing compounds (dialkyl ethers, alkyl ethers of polyhydric alcohols, etc.) and compounds in which at least some of the oxygen atoms in the oxygen-containing compound are replaced by S or Se. Examples of the polyhydric alcohol include alkylene glycols and polyalkylene glycols. Examples of the polyalkylene glycol include polyC _2-4 alkylene glycols such as ethylene glycol.

Specific examples of dialkyl ethers include methyl ethyl ether, diethyl ether, ethyl propyl ether, and propyl butyl ether. Specific examples of alkyl ethers of polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol diethyl ether. However, these are merely examples, and the second heteroatom-containing compound is not limited to these specific examples.

The first substituent that the aliphatic compound may have is not particularly limited and may be selected in consideration of the manufacturing method or application. Examples of the first substituent include a hydroxy group, an alkoxy group, an aliphatic acyloxy group, a carboxy group, an alkoxycarbonyl group, an aliphatic acyl group, a mercapto group, an alkylthio group, an amino group, an N-substituted amino group, a cyano group, a halogen atom, an oxo group (=O), and an S= group. The first element contained in the aliphatic compound may be substituted with an alkyl group or an alkyl group having a second substituent. These groups are also included in the first substituent. Examples of the alkyl group include a C _1-6 alkyl group or a C _1-4 alkyl group (such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group). Examples of the second substituent include a hydroxy group, an alkoxy group, an aliphatic acyloxy group, a mercapto group, an alkylthio group, an amino group, and an N-substituted amino group. However, these are merely examples, and the first and second substituents are not limited to these specific examples. The aliphatic compound may have one or more first substituents. When the aliphatic compound has two or more first substituents, at least two of the first substituents may be the same, or all of the first substituents may be different.

In addition, when the base portion has an aliphatic molecular chain, when focusing on each base portion, among the three first atoms (or second atoms) bonded to the three crosslinking chains, the one to which the second crosslinking chain is bonded is the first atom _a11 (or the second atom _a21 ), and for convenience, the molecular chain having two first atoms _a12 and _a13 (or second atoms _a22 and _a23 ) present on both ends so as to sandwich this first atom _a11 (or second atom _a21 ) is referred to as the first base portion (or second base portion). Here, there are no other first atoms between the first atom _a11 and each of the first atoms _a12 and _a13 . Similarly, there are no other second atoms between the second atom _a21 and each of the second atoms _a22 and _a23 .

When the first base part or the second base part includes a first organic ring, each base part may include one first organic ring, or may include two or more first organic rings linked by a single bond or a linking group. The first organic ring may be an alicyclic ring, an aromatic ring, or a condensed ring of an aliphatic ring and an aromatic ring. The alicyclic ring may have one or more carbon-carbon unsaturated bonds. The alicyclic ring may be a bridged ring. The first organic ring may be a hydrocarbon ring or a heterocycle containing a heteroatom (third heteroatom) as a ring constituent atom. Examples of the linking group include an alkylene group, an ether bond (-O-), a thioether bond (-S-), and a carbonyl group (-C(=O)-). Examples of the alkylene group constituting the linking group include, for example, a C _1-6 alkylene group. Specific examples of the alkylene group include, but are not limited to, a methylene group and a dimethylmethylene group.

Each first organic ring may, for example, be 3 or more members, 4 or more members, 5 or more members, or 6 or more members. Each first organic ring may, for example, be 20 or less members, 14 or less members, or 10 or less members. These lower and upper limits can be combined in any combination.

Examples of the first organic ring are explained below by classifying them into alicyclic hydrocarbons, aromatic hydrocarbons, fused cyclic hydrocarbons containing an aliphatic ring, and heterocycles.

Examples of alicyclic hydrocarbons include cycloalkanes, cycloalkenes, cycloalkadienes, cross-linked aliphatic hydrocarbons, and hydrogenated aromatic hydrocarbons described below. Specific examples of alicyclic hydrocarbons include cyclohexane, cyclohexene, decalin, norbornane, norbornene, adamantane, and dicyclopentadiene. However, these are merely examples, and the alicyclic hydrocarbons contained in each base part are not limited to these specific examples.

Aromatic hydrocarbons include arenes and bisaryls. Specific examples of arenes include benzene, toluene, xylene, naphthalene, phenanthrene, and anthracene. Specific examples of bisaryls include biphenyl, diphenyl ether, diphenyl thioether, diphenyl ketone, diphenylmethane, and dimethyldiphenylmethane. However, these are merely examples, and the aromatic hydrocarbons contained in each base part are not limited to these specific examples.

Fused cyclic hydrocarbons containing an aliphatic ring include those having a structure in which the above-mentioned aliphatic hydrocarbons and the above-mentioned aromatic hydrocarbons are condensed. Specific examples of such fused cyclic hydrocarbons include dihydronaphthalene, tetrahydronaphthalene, acenaphthene, and fluorene. However, these are merely examples, and fused cyclic hydrocarbons are not limited to these specific examples.

The third heteroatom that may be contained in the heterocycle may be Se, B, P, or Si, but is preferably at least one selected from the group consisting of O, S, and N. The heterocycle may have one third heteroatom, or may have two or more third heteroatoms. When the heterocycle contains two or more third heteroatoms, at least two of them may be the same, or all of the third heteroatoms may be different. The heterocycle may be a fused ring.

Specific examples of heterocycles include tetrahydrofuran, furan, dioxolane, tetrahydropyran, dioxane, chromene, tetrahydrothiophene, thiophene, tetrahydrothiopyran, pyrrolidine, pyrrole, imidazole, imidazoline, piperidine, pyridine, pyrimidine, indole, benzimidazole, quinoline, carbazole, oxazole, thiazole, morpholine, and thiazine. However, these are merely examples, and the heterocycle is not limited to these specific examples.

The first organic ring also includes those having a substituent (third substituent). In addition to those exemplified for the first substituent, examples of the third substituent include an aliphatic hydrocarbon group and an aliphatic hydrocarbon group having a substituent (fourth substituent). The aliphatic hydrocarbon group may be saturated or may have a carbon-carbon unsaturated bond. The aliphatic hydrocarbon group may be either linear or branched. Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but may be, for example, 1 to 26, 1 to 18 or 1 to 12, 1 to 10 or 1 to 6, or 1 to 4. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a 2-ethylhexyl group, and an n-octyl group. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a butenyl group. However, these are merely examples, and the third substituent is not limited to these specific examples. In addition, within the above range of carbon numbers, the lower limit of the number of carbon atoms in the alkenyl group is 2.

The fourth substituent can be selected from, for example, those exemplified for the first substituent, but is not limited thereto. The alkyl group may have one fourth substituent, or may have two or more fourth substituents. When the alkyl group has two or more fourth substituents, at least two of them may be the same, or all of the fourth substituents may be different.

The first organic ring may have one third substituent, or may have two or more third substituents. When the first organic ring has two or more third substituents, at least two of the third substituents may be the same, or all of the third substituents may be different.

From the viewpoint that each base portion becomes rigid and an asymmetric field is easily formed stably, it is preferable that the first organic ring contains at least an aromatic ring. From the same viewpoint, it is more preferable that both the first base portion and the second base portion contain at least an aromatic ring.

(Cross-linked chain)
The optically active compound has a plurality of crosslinking chains connecting the first base part and the second base part. The plurality of crosslinking chains include at least three, namely, the first crosslinking chain, the second crosslinking chain, and the third crosslinking chain. The number of crosslinking chains possessed by the optically active compound may be three or more, and may be determined according to the application (for example, the type and size of the metal or ion to be coordinated, the type and size of the compound to be included), etc. The upper limit of the number of crosslinking chains is not limited, but may be, for example, 6 or less, 5 or less, or 4 or less. The optically active compound may have three crosslinking chains. Each crosslinking chain other than the first to third crosslinking chains is also bonded to another first atom contained in the first base part and another second atom contained in the second base part.

Each of the first to third crosslinking chains is bonded to three first atoms contained in the first base portion and three second atoms contained in the second base portion. In this way, each crosslinking chain is bonded to a different first atom and a different second atom, and the first crosslinking chain and the second crosslinking chain are crossed, thereby forming an asymmetric field.

Each crosslinking chain may be a molecular chain (hydrocarbon chain) composed of a hydrocarbon, or may be a molecular chain containing a heteroatom (fourth heteroatom). The molecular chain containing the fourth heteroatom contains the fourth heteroatom in at least one of the side chain (including the substituent) and the main chain. The molecular chain containing the fourth heteroatom may be a hydrocarbon chain containing the fourth heteroatom in the side chain, or may be a molecular chain containing the fourth heteroatom in the main chain. Each of the hydrocarbon chain and the molecular chain containing the fourth heteroatom includes those having a substituent (fifth substituent). The fifth substituent is bonded to at least one of the main chain and the side chain of the hydrocarbon chain or the molecular chain containing the fourth heteroatom. The fourth heteroatom may be included in the fifth substituent. The structure of the crosslinking chain may be determined according to the type of the first atom and the second atom, the type of reaction for bonding these atoms to the crosslinking chain, and the like. When the optically active compound is coordinated to a metal or ion or is included in a compound, it is preferable that the crosslinking chain contains a fourth heteroatom from the viewpoint of facilitating interaction with the metal, ion, or compound. The type, position, and number of the fourth heteroatom in the crosslinked chain may be selected depending on the application (e.g., the type and size of the metal, ion, or compound, etc.).

The crosslinked chain is usually an aliphatic chain, but may be a molecular chain containing an aliphatic chain and an organic ring (second organic ring) in the main chain. The molecular chain containing the second organic ring may contain one or more aliphatic chains, and may contain one or more second organic rings. For example, the molecular chain containing the second organic ring may be composed of one second organic ring and one aliphatic chain, may be composed of two aliphatic chains and one second organic ring interposed between them, or may have a structure in which the aliphatic chain and the second organic ring are arranged alternately and repeatedly. When the crosslinked chain contains two or more aliphatic chains, at least two may be the same, or all of the aliphatic chains may be different. When the crosslinked chain contains two or more second organic rings, at least two may be the same, or all of the second organic rings may be different.

The second organic ring can be selected from, for example, those exemplified for the first organic ring. From the viewpoint of facilitating the interaction of the optically active compound with metals, ions, or compounds, the second organic ring is preferably a heterocycle, an organic ring having a third substituent containing a fourth heteroatom, or a fourth substituent containing a fourth heteroatom, among those exemplified for the first organic ring. The fourth heteroatom can be selected from the range described for the first heteroatom-containing compound. The fourth heteroatom contained in the third substituent or the fourth substituent is, for example, at least one of O, S, and N. Each bridging chain may contain one fourth heteroatom, or may contain two or more. In a bridging chain containing two or more fourth heteroatoms, at least two fourth heteroatoms may be the same, or all fourth heteroatoms may be different.

Examples of the fifth substituent include those exemplified for the first substituent, as well as groups containing an organic ring (third organic ring). Examples of the group containing the third organic ring include a monovalent group (R ^a -) corresponding to the third organic ring, an oxy group or a thio group (R ^a -O- or R ^a -S-) having a third organic ring, an acyloxy group (R ^a -C(=O)-O-) having a third organic ring, an oxycarbonyl group (R ^a -O-C(=O)-) having a third organic ring, an acyl group (R ^a -C(=O)-) having a third organic ring, and an N-substituted amino group (R ^a -NH-, (R ^a ) ₂ N-) in which the third organic ring is substituted with a nitrogen atom. R ^a - is a monovalent group corresponding to the third organic ring. In the N,N-disubstituted amino group (R ^a ) ₂ N-, the two R ^a's may be the same or different.

The third organic ring can be selected from those exemplified for the first organic ring. From the viewpoint of facilitating interaction of the optically active compound with metals, ions, or compounds, the third organic ring is preferably a heterocycle, an organic ring having a third substituent containing a fourth heteroatom, or an organic ring having a fourth substituent containing a fourth heteroatom, among those exemplified for the first organic ring.

The hydrocarbon chains included in the crosslinked chains include divalent groups corresponding to aliphatic hydrocarbons. The hydrocarbon chains may be either linear or branched. The hydrocarbon chains may be saturated or may have one or more carbon-carbon unsaturated bonds. Examples of aliphatic hydrocarbons corresponding to the hydrocarbon chains include alkanes, alkenes, alkadienes, and alkatrienes.

When the crosslinked ring does not include a second organic ring in the main chain, the crosslinked chain is composed of an aliphatic chain. In this case, the number of carbon atoms in the aliphatic hydrocarbon corresponding to the aliphatic chain is, for example, 8 or more, and may be 9 or more or 10 or more. In addition, the upper limit of the number of carbon atoms in the aliphatic hydrocarbon is not particularly limited, but may be, for example, 40 or less, 26 or less, 18 or less, or 16 or less. These lower and upper limits can be combined in any combination.

When the crosslinked chain contains an aliphatic chain and a second organic ring in the main chain, the lower limit of the number of carbon atoms in the aliphatic hydrocarbon corresponding to the aliphatic chain is not particularly limited, and may be 1 or more, 2 or more, 4 or more, 6 or more, or 8 or more, depending on the number of aliphatic chains contained in the crosslinked chain and the size and number of the second organic rings. The upper limit of the number of carbon atoms in the aliphatic hydrocarbon is, for example, 26 or less, and may be 18 or less, 16 or less, or 12 or less. These lower and upper limits can be combined in any manner.

In these aliphatic hydrocarbons, the number of carbon atoms may be selected according to the application of the optically active compound, within a range that allows the first crosslinking chain and the second crosslinking chain to cross. Specific examples of the aliphatic hydrocarbons include the aliphatic hydrocarbons exemplified for the base portion, as well as methane, ethane, dodecane, tetradecane, and hexadecane, but are not limited to these.

For a molecular chain containing a fourth heteroatom in the main chain, the explanations for the first heteroatom-containing compound and the second heteroatom-containing compound can be referred to for an aliphatic compound containing a fourth heteroatom in the main chain that corresponds to the aliphatic chain contained in the molecular chain.

When the bridged ring does not include a second organic ring in the main chain, the number of atoms in the main chain may be, for example, 8 or more, 9 or more, or 10 or more. The upper limit of the number of atoms in the main chain is not particularly limited, but may be, for example, 40 or less, 26 or less, 18 or less, or 16 or less. These lower and upper limits can be combined in any combination.

When the crosslinked chain contains a fourth heteroatom in the main chain and contains an aliphatic chain and a second organic ring, the lower limit of the number of atoms in the portion of the main chain of each aliphatic chain is not particularly limited, and may be 1 or more, or may be 2 or more, 4 or more, 6 or more, or 8 or more, depending on the number of aliphatic chains in the crosslinked chain and the size and number of the second organic rings. The upper limit of the number of atoms in the portion of the main chain of each aliphatic chain is, for example, 26 or less, and may be 18 or less, 16 or less, or 12 or less. These lower and upper limits can be combined in any manner.

The first crosslinking chain preferably includes a first unit represented by -X ¹ -R ¹ -. The second crosslinking chain preferably includes a second unit represented by -X ² -R ² -. R ¹ and R ² are each an alkylene group. X ¹ is a fourth heteroatom having a valence of 2, or a group represented by >X ^1a -R ^1a . Similarly, X ² is a fourth heteroatom having a valence of 2, or a group represented by >X ^2a -R ^2a . X ^1a and X ^2a are each a fourth heteroatom having a valence of 3. R ^1a and R ^2a are each a hydrogen atom, an alkyl group exemplified for the first substituent, or an alkyl group having a second substituent exemplified for the first substituent. The linking of the crosslinking chains forms two or more rings, and the first crosslinking chain and the second crosslinking chain each include a fourth heteroatom, which makes it easier to interact with metals, ions, or other compounds.

Each of ^X1 and ^X2 may be an oxygen atom, a sulfur atom, an imino group, or an N-substituted imino group. The substituent on the nitrogen atom of the N-substituted imino group is an alkyl group exemplified for the first substituent, or an alkyl group having a second substituent exemplified for the first substituent. Among them, when each of ^X1 and ^X2 is an oxygen atom or a sulfur atom (particularly an oxygen atom), an optically active compound can be produced relatively easily while ensuring high interactivity with metals, ions, or other compounds.

The number of carbon atoms in the alkylene group represented by ^R1 or ^R2 can be selected, for example, from the range of 1 to 40. The number of carbon atoms in the alkylene group may be 8 or more, 9 or more, or 10 or more. In addition, the number of carbon atoms in the alkylene group may be 40 or less, 26 or less, 18 or less, or 16 or less. These lower limit values and upper limit values can be combined in any desired manner.

The first crosslinking chain preferably contains a repeating structure of the first unit. Similarly, the second crosslinking chain preferably contains a repeating structure of the second unit. The first crosslinking chain and the second crosslinking chain contain such a repeating structure containing multiple fourth heteroatoms, making them flexible and stabilizing the crossed structure. In addition, such flexible crosslinking chains containing multiple fourth heteroatoms make them more likely to interact with metals, ions, or other compounds. Optically active compounds containing such first crosslinking chains and second crosslinking chains tend to act as multidentate ligands.

When each of the first crosslinking chain and the second crosslinking chain contains the repeating structure described above, the number of carbon atoms in the alkylene group represented by ^R1 or ^R2 in each unit is, for example, 2 to 4, and may be 2 or 3. Specific examples of the alkylene group include an ethylene group, a propylene group, and a trimethylene group.

The number of repetitions of the first unit in the first crosslinked chain is n1, and the number of repetitions of the second unit in the second crosslinked chain is n2. At this time, at least one of n1 and n2 is preferably 3 or more, and both are preferably 3 or more. Each of the repetition numbers n1 and n2 may be selected according to the application of the optically active compound within a range in which the first crosslinked chain and the second crosslinked chain can cross. Each of n1 and n2 may be 4 or more. The upper limit of each of n1 and n2 is not particularly limited, but may be, for example, 16 or less, 12 or less, or 10 or less. These lower limit values and upper limit values can be combined arbitrarily.

For the third crosslinking chain, the explanation for the first crosslinking chain or the second crosslinking chain can be referred to. The third crosslinking chain may be the same as or different from at least one of the first crosslinking chain and the second crosslinking chain. The third crosslinking chain may be a hydrocarbon chain, but is preferably a molecular chain containing a fourth heteroatom. The fourth heteroatom contained in the third crosslinking chain is preferably at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom.

The third crosslinking chain may contain a third unit represented by ^-X3 - ^R3- , or may contain a repeating structure of the third unit, similar to the first crosslinking chain or the second crosslinking chain. For ^X3 and ^R3 , see the explanations for ^X1 and ^R1 , respectively. The third crosslinking chain preferably contains a repeating structure of a third unit in which X3 is an oxygen atom (i.e., an oxyalkylene unit).

The repeat number n3 of the third unit may be selected from the range described for n1. The third crosslinking chain may cross other crosslinking chains as in the case of the first crosslinking chain and the second crosslinking chain, but it is preferable that it does not cross. When the third crosslinking chain does not cross other crosslinking chains, metals, ions, or other compounds are easily brought into close proximity to the ring formed by the base portion and the crosslinking chain. n3 may be selected according to the application of the optically active compound, and may be, for example, 12 or less, 10 or less, or 8 or less. These upper limits may be combined with the lower limits described for n1 in any combination.

The following formula (II) shows an example of an optically active compound in which the first base portion and the second base portion are benzene rings that may have a third substituent, and the first to third crosslinking chains have a repeating structure of an oxyalkylene unit.

ここで、Ｒ^ｂは、第３置換基であり、ｎｂは、各ベンゼン環におけるＲ^ｂの個数である。Ｒ^１～Ｒ^３、およびｎ１～ｎ３は、上述と同じである。各ベンゼン環のＲ^ｂは同じであってもよく、異なっていてもよい。各ベンゼン環についてｎｂは同じであってもよく、異なっていてもよい。

Here, R ^b is a third substituent, and nb is the number of R ^b in each benzene ring. R ¹ to R ³ and n1 to n3 are the same as above. R ^b in each benzene ring may be the same or different. n b for each benzene ring may be the same or different.

Since the optically active compound of the present invention has the structure described above, it is easy to obtain a high interaction with metals, ions, or other compounds. Therefore, the optically active compound can be coordinated to a metal or ion to form a coordination compound. In addition, the optically active compound has two or more ring structures composed of a base portion and a crosslinked chain. Such an optically active compound is sometimes called a cryptant (or optically active cryptant). The optically active compound can include other compounds to form an inclusion compound.

[Coordination Compounds]
The present invention also includes a coordination compound containing an ion or a metal and the above-mentioned optically active compound coordinated to the ion or the metal. The ion or the metal can be selected according to the application of the coordination compound. The coordination compound may contain at least one selected from an ion and a metal.

Metals include metals with an oxidation number of 0, such as palladium (0), nickel (0), and platinum (0). Ions include nonmetallic ions and metallic ions.

Examples of the nonmetallic ion include organic ammonium cations and ammonium ions. The organic ammonium cation can be selected depending on the size of the ring of the optically active compound, and examples of the organic ammonium cation include alkylammonium cations. The alkyl group in the alkylammonium cation also includes an alkyl group having a substituent (sixth substituent). Examples of the alkyl group include C _1-6 alkyl groups (ethyl group, propyl group, 2-propyl group, butyl group, etc.). The alkyl group may be linear or branched.

Examples of the sixth substituent include an aryl group, a hydroxy group, an alkoxy group, and an alkoxycarbonyl group. Examples of the aryl group include a C _6-14 aryl group (such as a phenyl group and a naphthyl group). The aryl group also includes an aryl group having a substituent (seventh substituent). Examples of the seventh substituent include a hydroxy group, an alkyl group, an alkoxy group, and an alkoxycarbonyl group. Examples of the alkyl group as the seventh substituent include a C _1-6 alkyl group (such as an ethyl group, a propyl group, a 2-propyl group, and a butyl group). Examples of the alkoxy group in the alkoxy group and alkoxycarbonyl group of the sixth and seventh substituents include a C _1-6 alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and a tert-butoxy group). The number of the sixth and seventh substituents may be one, or two or more.

Examples of metal ions include typical metal ions (e.g., metal ions of Groups 1, 2, and 12 to 16 of the periodic table) and transition metal ions. Specific examples of typical metal ions include lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, cesium ions, zinc ions, and aluminum ions. Specific examples of transition metal ions include vanadium ions, molybdenum ions, manganese ions, iron ions, ruthenium ions, rhodium ions, nickel ions, palladium ions, platinum ions, copper ions, silver ions, and gold ions. However, metal ions are not limited to these. The oxidation number of the metal ion may be selected depending on the application of the coordination compound.

A coordination compound may be a mononuclear complex containing one metal atom or metal ion per molecule, or a polynuclear complex containing two or more metal atoms or metal ions per molecule.

The coordination compound may have one of the above optically active compounds as a ligand in one molecule, or may have two or more. The coordination compound may have the above optically active compound as a first ligand and another ligand (second ligand). The second ligand may be a monodentate ligand or a multidentate ligand. The coordination compound may contain one second ligand in one molecule, or may contain two or more second ligands. When the coordination compound contains two or more second ligands in one molecule, at least two of the second ligands may be the same, or all of the second ligands may be different.

The second ligand is not particularly limited, but examples thereof include those containing a structure such as aqua, hydroxo, oxo, thiolato, sulfide, halo (chloro, bromo, etc.), hydride, cyanato, azide, thiocyanato, isocyanato, nitro, nitrito, carbonyl, carboxylato, oxalato, oxoanion, amine (ammine, triamine, tetramine, pyridine, triimine, etc.), phosphine (triarylphosphine (triphenylphosphine, etc.), trialkylphosphine, etc.), phosphate (including phosphate having a halogen atom (hexafluorophosphate, etc.)), borate (including borate having a halogen atom (tetrafluoroborate, etc.)), perchlorate, olefin (dibenzylideneacetone, cyclooctadiene, etc.), amino acid, or sugar.

The following formulas (II) and (III) show examples of a mononuclear complex containing one monovalent metal ion M 1 ⁺ and a binuclear complex containing two metal ions M 1 ⁺ , respectively.

ここで、Ｘ^－は、一価のカウンターアニオン（第２配位子）である。Ａ^１、Ａ^２、およびＣ１～Ｃ３は上述と同じである。

Here, X ⁻ is a monovalent counter anion (second ligand), and ^{A 1} , A ² , and C1 to C3 are the same as above.

[Method of producing optically active compound]
The optically active compound can be produced by a method for producing an optically active compound, which includes a step 1A for preparing a cyclic compound (first cyclic compound) in which the first base part and the second base part are linked by one of the first crosslinking chain and the second crosslinking chain, and the first base part and the second base part are not linked by the other of the first crosslinking chain and the second crosslinking chain, and a step 2A for linking the first base part and the second base part by the other of the first crosslinking chain and the second crosslinking chain so that the first crosslinking chain and the second crosslinking chain cross and overlap, thereby generating an asymmetric field. The production method that includes the steps 1A and 2A may be referred to as the A method.

Alternatively, the optically active compound can be produced by a method for producing an optically active compound, which includes a first step B for preparing a cyclic compound (second cyclic compound) in which the first base portion and the second base portion are linked by both the first crosslinking chain and the second crosslinking chain, and the first base portion and the second base portion are not linked by the third crosslinking chain, and a second step B for linking the first base portion and the second base portion by the third crosslinking chain, thereby crossing the first crosslinking chain and the second crosslinking chain, thereby generating an asymmetric field. The production method that includes the first step B and the second step B is sometimes referred to as the B method.

Processes 1A and 1B may be collectively referred to as Process 1, and Processes 2A and 2B may be collectively referred to as Process 2.

First, the second step will be described below.
(Second step)
In the second step, the first base portion and the second base portion can be linked by directly or indirectly (for example, via a fourth heteroatom) linking both ends of a crosslinked chain in a separately prepared chain compound containing a crosslinked chain to the first atom of the first base portion and the second atom of the second base portion, respectively. The first base portion and the second base portion can also be linked by forming a crosslinked chain by extending a chain at one of the first atom of the first base portion and the second atom of the second base portion, and linking the end of the grown crosslinked chain to the other. From the viewpoint of suppressing the variation in the chain length of the crosslinked chain, the former method is advantageous.

The linking between the crosslinking chain and each base part is carried out, for example, by using a reaction between a group containing the first atom and the second atom to which the crosslinking chain is bonded, or a group containing a fourth heteroatom bonded to these atoms, and an end group of a chain compound containing the crosslinking chain. Therefore, the end group of the chain compound may be selected according to the type of the group containing the first atom, the second atom, or the fourth heteroatom. In addition, a known reaction may be used for the above reaction for linking the crosslinking chain and each base part. For example, at least one selected from a coupling reaction, a nucleophilic substitution reaction, an electrophilic substitution reaction, an ester bond formation reaction, an amide bond formation reaction, a urethane bond reaction, an imine formation reaction, an olefin metathesis reaction, etc. may be used. These reactions may be combined with an elimination reaction.

For example, when an imine-forming reaction is used in the second step, a first cyclic compound having a formyl group in the first base portion and a formyl group in the second base portion can be reacted with a chain compound having primary amino groups at both ends to link the first base portion and the second base portion with a crosslinked chain. This reaction may be used in either step 2A or step 2B. When the first base portion and the second base portion are linked with a crosslinked chain using another reaction in the first step, it is advantageous to use an imine-forming reaction when introducing a third crosslinked chain in the second step.

In the second step, for example, a first cyclic compound having a hydroxy group in the first base portion and a hydroxy group in the second base portion is reacted with a chain compound having both ends as leaving groups, thereby linking the first base portion and the second base portion with a crosslinked chain. In the second step, for example, a compound having a leaving group bonded to the end of the other of the first and second crosslinked chains is used as the chain compound. In the second step, for example, a compound having a leaving group bonded to the end of the third crosslinked chain is used as the chain compound. The oxygen atom of the hydroxy group in the base portion corresponds to the fourth heteroatom. The ends of the crosslinked chain formed are bonded to the first atom and the second atom via oxygen atoms derived from the hydroxy group. Examples of reaction steps in the second step and the second step are shown below.

ここで、Ｌは、脱離基である。

Here, L is a leaving group.

As shown in the above reaction scheme, in step 2A, in a first cyclic compound (c1-1) in which the first base portion A1 and the second base portion A2 are linked by a first crosslinking chain C1 and a third crosslinking chain C3, the hydroxyl group of the first base portion A1 and the hydroxyl group of the second base portion A2 are reacted with a chain compound (c2-1) having a leaving group L at both ends of the second crosslinking chain C2, thereby linking by the second crosslinking chain C2. Similarly, in step 2B, in a second cyclic compound (c1-2) in which the first base portion A1 and the second base portion A2 are linked by a first crosslinking chain C1 and a second crosslinking chain C2, the hydroxyl group of the first base portion A1 and the hydroxyl group of the second base portion A2 are reacted with a chain compound (c2-2) having a leaving group L at both ends of the third crosslinking chain C3, thereby linking by the third crosslinking chain C3. Through these steps, an optically active compound (Ia-1) is formed.

The above reaction scheme shows an example of using a first cyclic compound (c1-1) having a structure in which the first base portion A1 and the second base portion A2 are linked by a first crosslinking chain C1, both ends of which are oxygen atoms (fourth heteroatom), and a third crosslinking chain C3, both ends of which are oxygen atoms (fourth heteroatom). Similarly, the second cyclic compound (c1-2) is an example of a structure in which the first base portion A1 and the second base portion A2 are linked by a first crosslinking chain C1, both ends of which are oxygen atoms (fourth heteroatom), and a second crosslinking chain C2, both ends of which are oxygen atoms (fourth heteroatom).

Examples of leaving groups (represented by L in the above reaction scheme) include tosyl, mesyl, trifluoromethylsulfonyl, nonafluorobutylsulfonyl, halogen atoms (I, Br, Cl, F, etc.), ester groups, and hydroxy groups. However, the invention is not limited to these, and the type of leaving group may be selected according to the type of the atom at the end of the crosslinked chain, the first atom, the second atom, or the fourth heteroatom bonded to these atoms.

The amount of the first chain compound is, for example, 0.8 to 1.2 moles, and may be 0.9 to 1.1 moles, per mole of the first cyclic compound. The amount of the second chain compound is, for example, 0.8 to 1.2 moles, and may be 0.9 to 1.1 moles, per mole of the second cyclic compound.

The second step is carried out, for example, in a solvent. Examples of the solvent include organic solvents. The solvent may be either a protic solvent or an aprotic solvent. Examples of the protic solvent include alcohols (ethanol, propanol, 2-propanol, etc.), nitro compounds (nitromethane, nitroethane, etc.), etc. Examples of the aprotic solvent include hydrocarbons (hexane, toluene, etc.), halogenated hydrocarbons (dichloromethane, chloroform, etc.), ethers (tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, etc.), esters (acetic esters, etc.), ketones (acetone, ethyl methyl ketone, etc.), nitriles (acetonitrile, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), sulfoxides (dimethyl sulfoxide, etc.), etc. The solvent may be used alone or in combination of two or more.

In the above reaction schemes [2A] and [2B], the second step may be carried out in the presence of a base. The base may be a tertiary amine (such as triethylamine), a metal hydroxide, or the like, but a metal carbonate is preferred. Examples of the metal carbonate include carbonates of alkali metals (specifically, Li, Na, K, Rb, Cs, and Fr) and carbonates of metals in Group 2 of the periodic table (Ca, Mg, and the like). Among these, alkali metal carbonates are preferred, and potassium carbonate, sodium carbonate, or cesium carbonate may be used. The base may be used alone or in combination of two or more types.

The amount of base is, for example, 2 to 4 moles, or may be 2.5 to 3.5 moles, per mole of the first cyclic compound or the second cyclic compound.

In order to efficiently proceed with the reaction in the second step, when the leaving group L is Cl, an alkali metal iodide (NaI, KI, CsI, etc.) may be introduced into the reaction system. When the second step is carried out in the presence of an alkali metal iodide, the leaving group L is converted from Cl to I, and the reaction can be accelerated.

The second step can be carried out under heating. The temperature of the second step is, for example, 50°C or higher and lower than the boiling point of the solvent, and may be 70 to 150°C or 80 to 120°C.

The time for heating in the second step is not particularly limited, but may be, for example, 1 hour or more and 200 hours or less, 6 hours or more and 150 hours or less, or 12 hours or more and 100 hours or less.

The second step can be carried out under atmospheric pressure, but may also be carried out under elevated or reduced pressure if necessary.

The reaction mixture obtained in the second step can be subjected to, for example, a known separation or purification method to obtain an optically active compound. Examples of the separation and purification methods include at least one selected from the group consisting of filtration, washing, extraction, distillation, crystallization, recrystallization, and chromatography.

When forming an optically active compound by Method B, it is also possible to preferentially form one enantiomer by selecting the chain length or structure of the crosslinking chain (particularly the first crosslinking chain and the second crosslinking chain), the type of base, etc. For example, by selecting the type or size of the metal ion contained in the base, it is possible to use the metal ion as a template or adjust the degree of interaction with the crosslinking chain. This makes it possible to control the three-dimensional configuration of the crosslinking chain and preferentially form one enantiomer.

The present invention also includes cyclic compounds such as the first cyclic compound or the second cyclic compound. Cyclic compounds are useful as precursors (or intermediates) for synthesizing optically active compounds. Among cyclic compounds, those in which the first base portion and the second base portion each contain an organic ring and the crosslinking chains each contain a repeating structure of an oxyalkylene unit are preferred. In particular, cyclic compounds including a first base portion, a second base portion, and two crosslinking chains connecting the first base portion and the second base portion are preferred. Note that one end of each of the two crosslinking chains is bonded to two first atoms of the first base portion, and the other end of each of the two crosslinking chains is bonded to two second atoms of the second base portion.

(First step)
In the first step, a first cyclic compound or a second cyclic compound is prepared. These cyclic compounds may be prepared by purchasing a commercial product, or may be prepared by synthesis using a known production method or a modified method thereof.

Each cyclic compound can be obtained, for example, by linking the first base part and the second base part with a crosslinking chain. Linking of the base parts with a crosslinking chain can be performed in a manner similar to that of the second step. Each cyclic compound can be obtained, for example, by directly or indirectly (e.g., via a fourth heteroatom) binding both ends of a crosslinking chain in a chain compound containing a crosslinking chain to a first atom of the first base part and a second atom of the second base part, respectively.

In the first step, two of the three first atoms of the first base part and two of the three second atoms of the second base part are linked by two crosslinking chains. Therefore, at least during the linking by the two crosslinking chains, the remaining one first atom (or second atom) or the fourth heteroatom bonded to this atom may be protected by a protecting group as necessary. Then, the first cyclic compound or the second cyclic compound from which the protecting group has been deprotected is subjected to the second step.

The protecting group is selected depending on the type of the first atom, second atom, or fourth heteroatom to be protected by the protecting group. For example, when a chain compound is reacted with the hydroxy group and the second hydroxy group of the first base part in the second step, the protecting group is a protecting group for the hydroxy group. Examples of such protecting groups include protecting groups that can be deprotected under reducing conditions (such as a benzyl group), protecting groups that can be deprotected under basic conditions (such as a benzoyl group or a 2,4,6-trimethylbenzoyl group), and protecting groups that can be deprotected under oxidizing conditions (such as a p-methoxybenzyl group).

The first cyclic compound (c1-1p) having a hydroxy group -O-Pro protected by a protecting group in the first base portion A1 and the second base portion A2 can be obtained, for example, by the reaction process shown in the following [1A]. The first cyclic compound (c1-1p) can be reduced, hydrolyzed, or oxidized to deprotect the protecting group Pro, thereby preparing the first cyclic compound (c1-1).

ここで、Ｌ^１およびＬ^２は脱離基である。

Here, ^L1 and ^L2 are leaving groups.

In reaction scheme [1A], a compound (b1p) including a first base portion A1 having a hydroxy group -O-Pro protected by a protecting group and two free hydroxy groups is reacted with chain compounds (c3-1) and (c3-2) to form a compound (b1p-c) in which a first crosslinking chain C1 and a third crosslinking chain C3 are bonded to the first base portion A1 via an oxygen atom (fourth heteroatom). Then, a first cyclic compound (c1-1p) is obtained by reacting this compound (b1p-c) with a compound (b2p) including a second base portion A2 having a hydroxy group -O-Pro protected by a protecting group and two free hydroxy groups.

The leaving group ^L1 and the leaving group ^L2 may be the same or different. From the viewpoint of prioritizing the reaction between the terminal on the leaving group ^L1 side and the compound (b1p) containing the first base portion over the leaving group ^L2 side, the leaving group ^L2 may be one having a lower leaving property than the leaving group ^L1 . For example, a chain compound (c3-1) (c3-2) containing a leaving group ^L1 containing a sulfonyl group and a leaving group ^L2 such as a halogen atom (I, Br, Cl, etc.) may be used.

The reaction of compound (b1p) with chain compounds (c3-1) and (c3-2), and the reaction of (b1p-c) with compound (b2p) can each be carried out in accordance with step 2. The reaction conditions can also be referenced to the conditions of step 2.

The second cyclic compound (c1-2) and the first cyclic compound in which the first base portion A1 and the second base portion A2 are connected by the second crosslinking chain C2 and the third crosslinking chain C3 can be obtained in the same manner as the first cyclic compound (c1-1).

The compound having the first base portion A1 and the compound having the second base portion A2 may be commercially available products, or may be synthesized by a known manufacturing method or a modified method thereof.

When the optically active compound has a substituent in the first base portion, the second base portion, or the crosslinked chain, the substituent can be introduced at an appropriate stage in the manufacturing process. If necessary, the above steps may be carried out while the substituent is protected with a protecting group, and the protecting group may be removed at an appropriate stage.

In reaction scheme [1A], the resulting compound (b1p-c) and compound (c1-1p) may be used in the next step as a reaction mixture as is, or may be separated or purified as necessary before being used in the next step. The separation or purification method may be selected from those described for the second step, for example.

The present invention also includes a compound in which molecular chains corresponding to two of the first to third crosslinking chains are bonded to the base portion (one of the base portions of the first base portion and the second base portion). Such a compound is useful as an intermediate for synthesizing an optically active compound (or a precursor for synthesizing the above-mentioned cyclic compound). Examples of such a compound include the above-mentioned compound (b1p-c) in which molecular chains corresponding to the first and third crosslinking chains are bonded to the base portion, a compound in which molecular chains corresponding to the second and third crosslinking chains are bonded to the base portion, and a compound in which molecular chains corresponding to the first and second crosslinking chains are bonded to the base portion. Among these, a compound in which the base portion contains an aromatic ring and the molecular chain contains a repeating structure of an oxyalkylene unit is preferable. One end of each of the two molecular chains is bonded to the two first atoms (or second atoms) of the base portion. The other end of the molecular chain may be the above-mentioned leaving group (such as a leaving group that can generate a hydroxyl group by elimination), a hydroxyl group, or a hydroxyl group protected by a protecting group. Examples of the protecting group include the above-mentioned hydroxyl group protecting groups.

[Example]
The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to the following examples.

The reaction steps for the synthesis of Example 1 are shown below.

ここで、Ｅｔは、エチル基であり、Ｂｎは、ベンジル基であり、Ｔｓは、トシル基である。

Here, Et is an ethyl group, Bn is a benzyl group, and Ts is a tosyl group.

Example 1 (Preparation of Optically Active Compound 9a by Method A)
(1) Synthesis of Compound 7a Compound 5a was synthesized according to the following procedure, and a first cyclic compound 7a having a hydroxy group protected by a benzyl group was synthesized using compound 5a.

10.0 g (34.7 mmol) of 4-benzyloxy-3,5-dihydroxybenzoic acid ethyl ester (compound 4) and 24.6 g (76.3 mmol) of 2-[2-(2-chloroethoxy)ethoxy]ethyl tosylate were dissolved in a mixture of 100 mL of acetonitrile and 33 mL of dimethylformamide (DMF). 12.0 g (86.8 mmol) of potassium carbonate was added to the resulting solution and stirred at 90°C for 22 hours. The solvent was distilled off from the resulting reaction mixture. The residue was neutralized with 10% by weight hydrochloric acid, and water was added. The resulting mixture was extracted three times with ethyl acetate, and the organic phase was collected. The organic phase was dried over sodium sulfate and concentrated. The concentrate was purified by silica gel chromatography to obtain 4-benzyloxy-3,5-bis{2-[2-(2-chloroethoxy)ethoxy]ethoxy}benzoic acid ethyl ester (compound 5a) (yield: 17.9 g, 88%). In the silica gel chromatography, a mixture of toluene/ethyl acetate = 5/1 (volume ratio) was used as the developing solvent.

The analytical results of compound 5a are as follows:
^1H NMR (500 MHz, _CDCl3 ) δ: 1.38 (t, J=7.1 Hz, 3H), 3.56-3.72 (m, 16H), 3.86-3.88 (m, 4H), 4.18-4.20 (m, 4H), 4.34 (q, J=7.2 Hz, 2H), 5.12 (s, 2H), 7.27-7.37 (m, 5H), 7.50-7.52 (m, 2H).

Compound 4 can be synthesized according to the method described in N. Michihata, Y. Kaneko, Y. Kasai, K. Tanigawa, T. Hirokane, S. Higasa, H. Yamada, J. Org. Chem. 2013, 78, 4319-4328.

10.0 g (17.0 mmol) of compound 5a and 4.90 g (17.0 mmol) of 3-benzoyloxy-4,5-dihydroxybenzoic acid ethyl ester (compound 3) were dissolved in 250 mL of DMF, to which 22.1 g (67.9 mmol) of cesium carbonate and 1.76 g (6.79 mmol) of cesium iodide were added. The resulting mixture was stirred at 100°C for 37 hours. The solvent was distilled off from the resulting reaction mixture. The residue was neutralized with 1% by mass hydrochloric acid, extracted three times with ethyl acetate, and the organic phase was recovered. The organic phase was dried over sodium sulfate and concentrated. The concentrate was purified by silica gel chromatography to obtain the first cyclic compound 7a (yield 2.35 g, 18%). In the silica gel chromatography, a mixture of toluene/acetone = 4/1 (volume ratio) was used as the developing solvent.

The analysis results of the first cyclic compound 7a are as follows.
^1H NMR (500 MHz, _CDCl3 ) δ: 1.37 (t, J=7.0 Hz, 6H), 3.62-3.81 (m, 18H), 4.14-4.24 (m, 6H), 4.34 (q, J=7.0 Hz, 4H), 5.08 (s, 2H), 5.15 (s, 2H), 7.29-7.32 (m, 5H), 7.35-7.39 (m, 5H), 7.44-7.46 (m, 4H).

Compound 3 was reported by A. Alam, Y. Takaguchi, H. Ito, T. Yoshida, S. Tsuboi, It can be synthesized according to the method described in Tetrahedron, 2005, 61, 1909-1918.

(2) Synthesis of the first cyclic compound, dihydroxy-dibenzo-25-crown-8 (compound 8a) 3.40 g (4.22 mmol) of compound 7a was dissolved in a mixed solvent of ethanol (62 mL) and chloroform (31 mL), and palladium carbon (palladium content 10 mass%) (0.55 g) was added. The mixture was stirred for 16 hours at room temperature (25°C) under a hydrogen stream. The resulting reaction mixture was filtered through Celite to remove the palladium carbon. The solvent was distilled off from the resulting solution. The residue was washed with diisopropyl ether to obtain the first cyclic compound 8a (white powder, yield 1.92 g, 73%).

The analysis results of the first cyclic compound 8a are as follows.
^1H NMR (300 MHz, _CDCl3 ) δ: 1.37 (t, J=6.3 Hz, 6H), 3.77-3.91 (m, 18H), 4.18-4.23 (m, 6H), 4.31 (q, J=6.3 Hz, 4H), 7.12 (br s, 1H), 7.28-7.31 (m, 4H), 7.33 (br s, 1H).

(3) Synthesis of optically active compound 9a 1.96 g (3.08 mmol) of the first cyclic compound 8a and 1.42 g (3.09 mmol) of triethylene glycol ditosylate were dissolved in 240 mL of DMF. 1.28 g (9.26 mmol) of potassium carbonate was added to the resulting solution, and the mixture was stirred at 95° C. for 58 hours. The solvent was distilled off from the resulting reaction mixture. The residue was neutralized with 10% by mass hydrochloric acid (25 mL), and water was added. The resulting mixture was extracted three times with ethyl acetate, and the organic phase was recovered. The organic phase was dried over sodium sulfate and concentrated. Compound 9a was separated from the concentrate by silica gel chromatography. In the silica gel chromatography, a mixture of dichloromethane/acetone = 4/1 (volume ratio) was used as a developing solvent. The separated compound 9a was purified by gel permeation chromatography (GPC) using chloroform as a developing solvent, further washed with diethyl ether, and the solvent was distilled off to obtain compound 9a (white powder, yield 0.97 g, 43%).

The analytical results of compound 9a are as follows:
^1H NMR (600 MHz, _C6D6 ) δ: 1.09 (t, J=6.0 Hz, _6H ), 3.31-3.35 (m, 4H), 3.40-3.50 (m, 12H), 3.62-.366 (m, 4H), 3.70-3.76 (m, 4H), 3.80-3.92 (m, 8H), 4.20 (q, J=6.0 Hz, 4H), 4.30-4.33 (m, 2H), 4.46-4.50 (m, 2H), 7.53 (d, J=1.8 Hz, 2H), 7.56 (d, J=1.8 Hz, 2H).

(4) Optical Resolution of Compound 9a Compound 9a obtained above was optically resolved using chiral high performance liquid chromatography (HPLC). It was confirmed that the compound 9a could be separated into a compound with a positive specific rotation and a compound with a negative specific rotation, and that the absolute values of the compounds were almost the same.

The reaction scheme for synthesizing compound 9a from compound 6a in Example 2 is shown below.

ここで、Ｅｔは、エチル基であり、Ｂｎは、ベンジル基であり、Ｔｓは、トシル基である。

Here, Et is an ethyl group, Bn is a benzyl group, and Ts is a tosyl group.

Example 2 (Synthesis of optically active compound 9a by Method B)
(1) Synthesis of Compound 6a [0123] Except for using Compound 3 instead of Compound 4, the same procedure as for Compound 5a in Example 1(1) was followed to obtain 2-benzyloxy-3,4-bis{2-[2-(2-chloroethoxy)ethoxy]ethoxy}benzoic acid ethyl ester (Compound 6a).

The analytical results of compound 6a are as follows:
^1H -NMR (500 MHz, _CDCl3 ) δ: 1.38 (t, J = 7.2 Hz, 3H), 3.51-3.97 (m, 20H), 4.21-4.25 (m, 4H), 4.35 (q, J = 7.2 Hz, 2H), 5.14 (s, 2H), 7.30-7.34 (m, 2H), 7.34-7.37 (m, 3H),7.44-7.47 (m, 2H).

(2) Synthesis of Compounds 10a and 11a A solution was prepared by dissolving 1.82 g (3.10 mmol) of Compound 6a and 0.89 g (3.10 mmol) of Compound 3 in 100 mL of DMF. 3.03 g (9.30 mmol) of cesium carbonate and 0.40 g (1.55 mmol) of cesium iodide were added to the obtained solution, and the mixture was stirred at 100° C. for 63 hours. The solvent was distilled off from the obtained reaction mixture, and the mixture was acidified by adding hydrochloric acid having a concentration of 1% by mass, and then extracted three times with ethyl acetate to recover the organic phase. The organic phase was dried with sodium sulfate. A solid was obtained by distilling off the solvent from the organic phase. The obtained solid was washed with ethanol and dried to obtain dibenzyloxy-DB24crown-8 (a mixture of Compound 10a and Compound 11a) (yield 850 mg, yield 34%), which is a second cyclic compound in which the hydroxyl group is protected by a benzyl group. The molar ratio of compounds 10a and 11a in the mixture was 1:1.

The formation of the mixture was confirmed by ¹ H-NMR, and the analytical results are as follows.
^1H -NMR (500 MHz, _CDCl3 ) δ: 7.51-7.27 (m, 14H), 5.13 (s, 4H, Ar- _OCH2Ph ), 4.34 (q, J = 7.2 Hz, 4H _, -CO2CH2CH3), 4.29-4.10 (m, 8H _{) ,} 3.98-3.69 (m, _16H ), 1.37 (t, J = 7.2 Hz, 6H _{, -CO2CH2CH3} ).

(3) Synthesis of second cyclic compounds 12a and 13a 0.430 g (0.53 mmol) of the mixture of compounds 10a and 11a obtained in (2) above was dissolved in 30 mL of ethanol and 15 mL of chloroform. 0.121 g of palladium carbon (palladium content 10% by mass) was added to the obtained solution. The mixture was stirred for 69 hours at room temperature (25° C.) under a hydrogen stream. The palladium carbon was removed by filtering the obtained reaction mixture through Celite. The solvent was distilled off from the obtained solution. The second cyclic compound 12a was separated from the obtained residue using silica gel chromatography. In the silica gel chromatography, the mixture was purified using a mixture of chloroform: toluene: ethyl acetate = 1: 1: 1 (volume ratio), a mixture of chloroform: toluene: ethyl acetate = 1: 1: 2 (volume ratio), and a mixture of ethyl acetate in that order. From the fraction eluted with chloroform:toluene:ethyl acetate=1:1:1 (volume ratio), a second cyclic compound, dihydroxy-DB24 crown 8 (compound 12a) (yield: 0.136 g, 41%) was obtained. From the fraction eluted with chloroform:toluene:ethyl acetate=1:1:2 (volume ratio) and ethyl acetate, a second cyclic compound, dihydroxy-DB24 crown 8 (compound 13a) (yield: 0.146 g, 44%) was obtained.

The formation of compounds 12a and 13a was confirmed by ¹ H-NMR. The analytical results are as follows.
Compound 12a:
^1H -NMR (300 MHz, _CDCl3 ) δ: 7.67-7.65 (br, 2H, -OH), 7.24 (d, J = 1.8 Hz, 2H), 7.11 (d, J = 1.8 Hz, 2H), 4.33 (q, J = 7.1 Hz, 4H, _CH2 moiety _of -CO2CH2CH3), 4.26-4.18 (m, 4H), 4.18-4.09 (m, _4H ) _, 3.89-3.71 (m, 16H), 1.37 (t, J = 7.1 Hz, 6H _{, CH3} moiety of _-CO2CH2CH3 ) _.

Compound 13a:
^1H -NMR (500 MHz, _CDCl3 ) δ: 1.37 (t, J=7.1 Hz, 6H), 3.69 (s, 4H), 3.77 (s, 4H), 3.79-3.81 (m, 4H), 3.82-3.84 (m, 4H), 4.19-4.21 (m, 4H), 4.23-4.25 (m, 4H), 4.33 (q, J=7.1 Hz, 4H), 6.98 (br s, 2H), 7.16 (d, J = 1.8 Hz, 2H), 7.29 (d, J=1.8 Hz, 2H).

(4) Synthesis of Optically Active Compound 9a 80 mg (0.13 mmol) of the second cyclic compound 12a obtained in (3) above and 59 mg (0.13 mmol) of triethylene glycol ditosylate were dissolved in 16 mL of DMF. 53 mg (0.38 mmol) of potassium carbonate was added to the resulting solution, and the mixture was stirred at 95° C. for 43 hours. The solvent was distilled off from the resulting reaction mixture, and the residue was neutralized with 10% by mass hydrochloric acid, and water was added. The resulting mixture was extracted three times with ethyl acetate, and the organic phase was recovered. The organic phase was dried with sodium sulfate. The solvent was distilled off from the organic phase. The resulting residue was purified by GPC to obtain compound 9a (yield 56 mg, yield 59%).

The formation of compound 9a was confirmed by ¹ H-NMR. The analytical results are as follows.
^1H -NMR (600 MHz, _CDCl3 ) δ: 4.39-4.33 (m, 6H), 4.28-4.18 (m, 8H), 4.06-4.00 (m, 2H), 3.93-3.60 (m, 24H), 1.38 (t, J = 6.9 Hz, 6H).

(5) Optical Resolution of Compound 9a Compound 9a obtained above was optically resolved using chiral high performance liquid chromatography (HPLC). It was confirmed that the compound 9a could be separated into a compound with a positive specific rotation and a compound with a negative specific rotation, and that the absolute values of the compounds were almost the same.

Example 3 (Evaluation of chiral amine recognition by compound 9a)
The compounds with positive and negative specific rotations obtained by optical resolution in Example 1 or Example 2 were dissolved in chloroform or a mixture of chloroform/acetonitrile = 1/1 (volume ratio) to obtain a solution, to which (S)-1-phenylethylammonium ClO ₄ salt, (R)-1-phenylethylammonium ClO ₄ salt, (S)-1-(1-naphthyl)ethylammonium ClO ₄ salt, L-phenylalanine benzyl ether HClO ₄ salt, and (S)-2-phenylglycinol HClO ₄ salt were added, and the signal change in the ¹ H-NMR spectrum of compound 9a was tracked. From the signal change at this time, the association constant between compound 9a and the guest was determined. As a result, a difference of 1.1 to 1.5 times was observed in the first-stage association constants of the compounds with negative and positive specific rotations with respect to the optically active ammonium salt, and a difference of 1.0 to 3.0 times was observed in the second-stage association constants.

Example 4 (Evaluation of sodium ion and potassium ion recognition by compound 9a)
The sodium ion and potassium ion recognition ability of compound 9a synthesized in Example 1 or Example 2 was evaluated by the following procedure.
Racemic compound 9a was dissolved in a mixture of acetonitrile, methanol/acetonitrile, or dimethylsulfoxide/acetonitrile to prepare solutions containing compound 9a at concentrations of 40 μmol/L to 100 μmol/L. NaClO ₄ or KClO ₄ was added to these solutions in amounts ranging from 10 to 300 equivalents, and the change in the ultraviolet-visible-near infrared spectrum was measured. From the signal change at this time, the interaction between compound 9a and sodium ions or potassium ions was confirmed, and it was also recognized that sodium ions and potassium ions recognize two metal ions in a stepwise manner. It was also recognized that the association constants of the second stage of both metal ions were greatly reduced compared to the association constants of the first stage.

The optically active compound of the present invention has an asymmetric field formed by a structure in which molecular chains overlap to cross. Due to this special structure, it can be used in various applications such as asymmetric reactions, asymmetric catalytic reactions, medicines, chemical products, packing materials for chiral column chromatography, liquid crystal displays, lens filters, etc. However, these applications are merely examples, and the applications of the optically active compound are not limited to these.

Claims (8)

a first base portion, a second base portion, and a plurality of cross-linking chains connecting the first base portion and the second base portion;
the plurality of crosslinked chains include at least three of a first crosslinked chain, a second crosslinked chain, and a third crosslinked chain;
one end of each of the first crosslinking chain, the second crosslinking chain, and the third crosslinking chain is bonded to three first atoms having a valence of three or more contained in the first base portion;
the other ends of the first crosslinking chain, the second crosslinking chain and the third crosslinking chain are bonded to three second atoms having a valence of three or more contained in the second base portion;
the first crosslinking chain includes a repeating structure of a first unit represented by -O-R ¹ - (wherein R ¹ is an alkylene group);
the second crosslinking chain includes a repeating structure of a second unit represented by -O-R ² - (wherein R ² is an alkylene group);
the third crosslinking chain includes a repeating structure of a third unit represented by -O-R ³ - (wherein R ³ is an alkylene group);
where n1 is the number of repetitions of the first unit in the first crosslinked chain, n2 is the number of repetitions of the second unit in the second crosslinked chain, and n3 is the number of repetitions of the third unit in the third crosslinked chain, each of n1, n2, and n3 is 16 or less;
the first crosslinked chain and the second crosslinked chain are overlapped so as to cross each other, thereby generating an asymmetric field ;
The following formula (ia):

(In the formula, R ^b is a substituent, and n b is the number of R ^b in each benzene ring. R ^b in each benzene ring may be the same or different. n b for each benzene ring may be the same or different.)
An optically active compound represented by the formula: 2. The optically active compound according to claim 1 , wherein at least one of n1 and n2 is 3 or more. The optically active compound according to claim 2 , wherein both n1 and n2 are 3 or more and 16 or less. A coordination compound comprising an ion or a metal, and the optically active compound according to any one of claims 1 to 3 coordinated to the ion or the metal. A method for producing the optically active compound according to any one of claims 1 to 3 , comprising the steps of:
a first crosslinking chain and a second crosslinking chain, and the first base portion and the second base portion are connected to each other by the third crosslinking chain, and the first base portion and the second base portion are not connected to each other by the other of the first crosslinking chain and the second crosslinking chain;
and a step 2A of linking the first base portion and the second base portion at the other of the first crosslinking chain and the second crosslinking chain so that the first crosslinking chain and the second crosslinking chain cross and overlap, thereby generating an asymmetric field. the first cyclic compound has a hydroxy group on the first base portion and a hydroxy group on the second base portion;
6. The method for producing an optically active compound according to claim 5, wherein in step 2A, a chain compound containing the other crosslinked chain and having leaving groups at both ends is reacted with the first cyclic compound to link the first base portion and the second base portion via the other crosslinked chain. A method for producing the optically active compound according to any one of claims 1 to 3 , comprising the steps of:
a step 1B of preparing a second cyclic compound in which the first base portion and the second base portion are linked by both the first crosslinked chain and the second crosslinked chain, and the first base portion and the second base portion are not linked by the third crosslinked chain;
and a second step B of connecting the first base portion and the second base portion with the third crosslinking chain, thereby crossing the first crosslinking chain and the second crosslinking chain to generate an asymmetric field. the second cyclic compound has a hydroxy group on the first base portion and a hydroxy group on the second base portion;
8. The method for producing an optically active compound according to claim 7, wherein in step 2B, a chain compound including the third crosslinking chain and having leaving groups at both ends is reacted with the second cyclic compound to link the first base portion and the second base portion via the third crosslinking chain.