JPS5927345B2 - Optically active cyclopentane compound and method for producing the same - Google Patents
Optically active cyclopentane compound and method for producing the sameInfo
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- JPS5927345B2 JPS5927345B2 JP1392980A JP1392980A JPS5927345B2 JP S5927345 B2 JPS5927345 B2 JP S5927345B2 JP 1392980 A JP1392980 A JP 1392980A JP 1392980 A JP1392980 A JP 1392980A JP S5927345 B2 JPS5927345 B2 JP S5927345B2
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Description
【発明の詳細な説明】
本発明は、構造式：
で表わされる新規な光学活性シクロペンタン化合物及び
その製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel optically active cyclopentane compound represented by the structural formula: and a method for producing the same.
天然には、プロスタグランジン
（ＰｒＯｓｔａｇｌａｎｄｉｎ）類やブレフエルジン（
Ｂｒｅｆｅｌｄｌｎ）に代表されるように、光学活性シ
クロペンタンを母核とする生理活性物質が多数存在する
。Naturally, prostaglandins (PrOstaglandin) and brefeldin (
There are many physiologically active substances that have optically active cyclopentane as their core, as typified by (Brefeldln).
特にプロスタグランジンは、動物の各組織に存在し、生
体内で分泌され、微量で平滑筋、血圧、脂質代謝等に作
用するホルモンとして注目されており、治療への応用と
して、降圧利尿剤、血栓治療剤、気管支拡張剤、潰瘍治
療剤、陣痛促進剤及び動脈硬化予防剤等の種々の医薬と
しての利用が期待されている。本発明の光学活性シクロ
ペンタン化合物は、これら生理活性物質、特にプロスタ
グランジン類を合成する際の重要な中間体として有用で
ある。In particular, prostaglandins are present in various tissues of animals, are secreted in vivo, and are attracting attention as hormones that affect smooth muscle, blood pressure, lipid metabolism, etc. in minute amounts. It is expected to be used as a variety of medicines such as thrombotic therapeutics, bronchodilators, ulcer therapeutics, labor promoters, and arteriosclerosis preventive agents. The optically active cyclopentane compound of the present invention is useful as an important intermediate in the synthesis of these physiologically active substances, especially prostaglandins.
例えば、プロスタグランジンＨ２の類似化合物で、その
数倍の大動脹収縮活性を有する下記の構造式で示される
化合物〔Ｅ〕を、次の工程によつて合成することができ
る。以下に、本発明を詳述する。For example, a compound [E] represented by the following structural formula, which is a similar compound to prostaglandin H2 and has several times the large diastolic contraction activity, can be synthesized by the following steps. The present invention will be explained in detail below.
まず、本発明の出発物質は、
メチル２
デオキシ−２−Ｃ−シアノメチル−β−Ｄ−アラビノー
ヘキソフラノシド（Ｍｅｔｈｙｌ２，３−ｄｉｄｅｏｘ
ｙ−２−Ｃ−ｃｙａｎｏｍｅｔｈｙｌ −β−Ｄａｒａ
ｂｉｎｏ−ｈｅｘｏｆｕｒａｎｏｓｉｄｅ）〔１〕であ
り、例えば次の工程によつて得ることができる。First, the starting material of the present invention is Methyl2,3-dideox-2-C-cyanomethyl-β-D-arabinohexofuranoside
y-2-C-cyanomethyl-β-Dara
bino-hexofuranoside) [1], and can be obtained, for example, by the following process.
すなわち、Ｄ−グルコースより誘導されるメチル５，６
−０−シクロヘキシリデン−３−０−メシルーβ−Ｄ−
アロフラノシド（ｍｅｔｈｙｌ５，６０−ｃｙｃｌｏｈ
ｅｘｙ１１ｄｅｎｅ−３−０−ｍｅｓｙｌ−β−Ｄ−ａ
ｒｏｆｕｒａｎｏｓｉｄｅ）〔Ａ〕（Ｍ．Ｋａｗａｎａ
ａｎｄＳ−ＥｍｏｔｏりＢｕｌｌ−Ｃｈｅｍ・Ｓｏｃ．
Ｊａｐａｎ ５３，２２２−２２９（１９８０）参照。
）を、テトラヒドロフラン中、室温で一夜５当量のリチ
オジメチルシアノメチルホスホネー卜（ｌｉｔｈｉｏｄ
ｉｍｅｔｈｙｌｃｙａｎｏｍｅｔｈｙｌｐｈｏ一ｎａｔ
ｅ）で処理すると、２つの化合物、メチル５，６−０−
シクロヘキシリデン−２，３−ジデオキシ−２−Ｃ−シ
アノメチリデンーβ−Ｄ−エリスローヘキソフラノシド
（ｍｅｔｈｙｌ５，６−０ＣｙＣ１０ｈｅｘｙｌｉｄｅ
ｎｅ−２，３−ｄｉｄｅｏｘｙ−２−Ｃ−ｃｙａｎｏｍ
ｅｔｈｙｌｉｄｅｎｅ−β−Ｄ−ｅｒｙｔｈｒｏ−ｈｅ
ｘｏｆｕｒａｎｏｓｉｄｅ）〔Ｂ〕とメチル５，６−シ
クロヘキシリデン−２，３−ジデオキシ−２，３−ジデ
ヒドロ−２−Ｃ−シアノメチルーβ−Ｄ−エリスローヘ
キソフラノシド（ｍｅｔｈｙ１５２６−ｃｙｃｌｏｈｅ
ｘｙｌｉｄｅｎｅ−２ラ３−ｄｉｄｅｏｘｙ−２，３−
ｄｉｄｅｈｙｄｒｏ−２−Ｃ一ｃｙａｎｏｍｅｔｈｙｌ
−β−Ｄ−ｅｒｙｔｈｒｏｈｅｘｏｆｕｔａｎｏｓｉ
ｄｅＣＣ〕が約１：９の混合物として得られる。That is, methyl 5,6 derived from D-glucose
-0-cyclohexylidene-3-0-mesyl-β-D-
Allofuranoside (methyl5,60-cycloh
exy11dene-3-0-mesyl-β-D-a
rofuranoside) [A] (M.Kawana
andS-EmotoriBull-Chem・Soc.
See Japan 53, 222-229 (1980).
) in tetrahydrofuran overnight at room temperature.
imethylcyanomethylpho-nat
Upon treatment with e), two compounds, methyl 5,6-0-
Cyclohexylidene-2,3-dideoxy-2-C-cyanomethylidene-β-D-erythrohexofuranoside (methyl5,6-0CyC10hexylide
ne-2,3-dideoxy-2-C-cyanom
ethylidene-β-D-erythro-he
xofuranoside) [B] and methyl 5,6-cyclohexylidene-2,3-dideoxy-2,3-didehydro-2-C-cyanomethyl-β-D-erythrohexofuranoside (methyl1526-cyclohe
xylidene-2 la 3-dideoxy-2,3-
didehydro-2-C-cyanomethyl
-β-D-erythrohexofutanosi
deCC] is obtained as a mixture of about 1:9.
これら２つの化合物は、シリカゲルカラムクロマトグラ
フイーにより、それぞれ分離することができる。These two compounds can be separated by silica gel column chromatography.
得られた化合物〔Ｂ〕と〔Ｃ〕を、１０％ＰｂーＣで接
触還元すると、単一の生成物であるメチル５，６−０−
シクロヘキシリデン−２，３−ジデオキシ−２−Ｃ−シ
アノメチルーβ−Ｄ−アラビノ一ヘキソフラノシド（ｍ
ｅｔｈｙｌ５，６−０ーｃｙｃ１０ｈｅｘｙｌｉｄｅｎ
ｅ−２，３−ｄｉｄｅｏｘｙ−２ーＣ−ｃｙａｎｏｍｅ
ｔｈｙｌ −β−Ｄ−ａｒａｂｉｎｏーｈｅｘｏｆｕｒ
ａｎｏｓｉｄｅ）〔Ｄ〕を定量的に得る。When the obtained compounds [B] and [C] are catalytically reduced with 10% Pb-C, a single product, methyl 5,6-0-
Cyclohexylidene-2,3-dideoxy-2-C-cyanomethyl-β-D-arabinomonohexofuranoside (m
ethyl5,6-0-cyc10hexylidene
e-2,3-dideoxy-2-C-cyanome
thyl-β-D-arabino-hexofur
anoside) [D] is obtained quantitatively.
得られた化合物〔Ｄ〕の５，６−０−シクロヘキシリデ
ン部分を７０％酢酸水溶液で選択的に加水分解を行うと
、本発明の出発物質化合物〔１〕を、ほぼ定量的に得る
ことができる。かくして得られた化合物〔１〕を出発物
質として、次の工程により本発明の光学活性シクロペン
タン化合物を合成することができる。When the 5,6-0-cyclohexylidene moiety of the obtained compound [D] is selectively hydrolyzed with a 70% acetic acid aqueous solution, the starting material compound [1] of the present invention can be obtained almost quantitatively. I can do it. Using the thus obtained compound [1] as a starting material, the optically active cyclopentane compound of the present invention can be synthesized through the following steps.
すなわち、化合物〔１〕を、Ｐ−トルエンスルホン酸ク
ロライドで処理してトシル化し、モノトンレート体のメ
チル２，３−ジデオキシ−２−Ｃーシアノメチル−６−
０−トシル一β−Ｄ−アラビノーヘキソフラノシド（Ｍ
ｅｔｈｙｌ２，３−ＤｉｄｅＯｘｙ−２−Ｃ−Ｃｙａｎ
Ｏｍｅｔｈｙｌ−６−０一ＴＯｓｙｌ−β−Ｄ−Ａｒａ
ｂｉｎＯ−ＨｅｘＯｆｕｒａｎＯｓｉｄｅ）〔〕を得る
ｏ溶媒としては、ピリジンが最適である。That is, compound [1] is treated with P-toluenesulfonic acid chloride to tosylate, and the monotonate methyl 2,3-dideoxy-2-C-cyanomethyl-6-
0-Tosyl-β-D-arabinohexofuranoside (M
ethyl2,3-DideOxy-2-C-Cyan
Omethyl-6-0-TOsyl-β-D-Ara
Pyridine is optimal as the solvent for obtaining binO-HexOfuranOside) [].
又、反応温度は室温で充分であり、反応時間は約２〜３
時間が適当である。得られたモノトンレート体〔〕をア
ルカリで処理してエポキシ化を行つて、メチル５，６−
アンヒトロー２，３−ジデオキシ−２−Ｃ−シアノメチ
ル−β−Ｄ−アラビノーヘキソフラノシド（Ｍｅｔｈｙ
ｌ５，６−ＡｎｈｙｄｒＯ−２，３一ＤｉｄｅＯｘｙ−
２−Ｃ−ＣｙａｎＯｍｅｔｈｙｌ−β−Ｄａｒａｂｉｎ
Ｏ−ＨｅｘＯｆｕｒａｎＯｓｉｄｅ）〔〕を得る。In addition, the reaction temperature is sufficient at room temperature, and the reaction time is about 2 to 3 minutes.
The time is appropriate. The obtained monotonlate compound [ ] was treated with an alkali to perform epoxidation to obtain methyl 5,6-
Anthitro 2,3-dideoxy-2-C-cyanomethyl-β-D-arabinohexofuranoside (Methy
l5,6-AnhydrO-2,3-DideOxy-
2-C-CyanOmethyl-β-Darabin
O-HexOfuranOside) [] is obtained.
アルカリとしては、ＮａＯＣＨ３，ＤＢＵ，ＤＢＮが適
当であり、又溶媒としては、ジクロルメタン、テトラヒ
ドロフラン、ベンゼンが適当である。Suitable alkalis include NaOCH3, DBU, and DBN, and suitable solvents include dichloromethane, tetrahydrofuran, and benzene.
反応温度は、室温で充分であり、反応時間は、約３０分
〜１時間が適当である。得られたエポキシ体〔〕を、り
チオ ヘキサメチルジシラジド（１ｉｔｈ０ｈｅｘａｍ
ｅｔｈｙ１ｄｉｓｉ１ａｚｉｄｅ）〔あらかじめ、ヘキ
サメチルジシラザン（Ｈｅｘａｍｅｔｈｙｌｄｉｓｉｌ
ａｚａｎｅ）とブチル リチウム（Ｂｕｔｙｌｌｉｔｈ
ｉｕｍ）によつて調製したもの〕で処理すると、分子内
開環が起り、１（８）−オキソ３（Ｒ）−メトキシ−４
（Ｒ）、５（Ｓ）−シアノー７（Ｒ）ーヒドロキシビシ
クロ〔３，２，１〕オクタン（１′１（Ｓ）−０ｘ０−
３（Ｒ）−ＭｅｔｈＯｘｙ−４（Ｒ）、５（Ｓ）一Ｃｙ
ａ−ＮＯ−７（Ｒ卜土ＹｄｒＯｘｙｂｉｃｙｃｌＯ〔３
，２，１〕０ｃｔａｎｅ〔Ｖ〕と１（Ｓ）−２−オキソ
一３（Ｒ）−メトキシ−４（Ｒ）、５（Ｓ）−シアノ−
６（Ｒ）−ヒドロキシメチルビシクロ〔２，２，１〕ヘ
プタン１Ｃ１（Ｓ）−２−０ｘ０−３（Ｒ）−Ｍｅｔｈ
Ｏｘｙ−４（Ｒ）、５（Ｓ）一ＣｙａｎＯ−６（Ｒ）Ｈ
ｙｄｒＯｘｙｍｅｔｈｙｌｂｉｃｙｃｌＯ〔２ツ２，１
〕Ｈｅｐｔａｎｅ〔〕の約１：１の混合物を得る。Room temperature is sufficient for the reaction temperature, and a suitable reaction time is about 30 minutes to 1 hour. The obtained epoxy body [] was converted into lithiohexamyl disilazide
ethy1disilazide) [Hexamethyldisilazane (Hexamethyldisilazane)
azane) and butyl lithium (butyllithium).
ium)], intramolecular ring opening occurs and 1(8)-oxo3(R)-methoxy-4
(R), 5(S)-cyano7(R)-hydroxybicyclo[3,2,1]octane (1'1(S)-0x0-
3(R)-MethOxy-4(R),5(S)-Cy
a-NO-7(R
,2,1]0ctane[V] and 1(S)-2-oxo-3(R)-methoxy-4(R),5(S)-cyano-
6(R)-Hydroxymethylbicyclo[2,2,1]heptane 1C1(S)-2-0x0-3(R)-Meth
Oxy-4(R), 5(S)-CyanO-6(R)H
ydrOxymethylbicycleO [2 pieces 2,1
]Heptane[] approximately 1:1 mixture is obtained.
この混合物を、シリカゲルカラムクロマトグラフイ一に
付し、ＣＨＣｌ３−ＣＨ３ＯＨ（５０：１／）で溶出す
ると、先に化合物〔Ｖ〕が溶出し、次いで、本発明の目
的化合物〔〕が溶出する。When this mixture is subjected to silica gel column chromatography and eluted with CHCl3-CH3OH (50:1/), compound [V] is eluted first, followed by the target compound of the present invention [].
以下、本発明を実施例によつて説明するが、化合物（）
．（Ｍ），（ＩＶ），（は、いずれも新規化合物である
。化合物〔１〕（１９）とＰ−トルエンスルホン酸クロ
ライド（１９）をピリジン（２０ｍ０中、室温で一夜攪
拌した。Hereinafter, the present invention will be explained with reference to Examples, and the compound ()
．． (M), (IV), ( are all new compounds. Compound [1] (19) and P-toluenesulfonic acid chloride (19) were stirred in pyridine (20 mO) at room temperature overnight.
減圧下で溶媒を留去するとシロツプ状物質が得られ、こ
れをシリカゲルカラムクロマトグラフイ一に付した。Ｃ
ＨＣｌ３ＣＨ３ＯＨ（２０：１ｖ／ｖ）で溶出すると、
シロツプ状の化合物〔〕（１．５９、収率８５％）が得
られた。実施例 ２
メチル５，６−アンヒトロー２，３−ジデオキシ−２−
Ｃ−シアノメチル−β−Ｄ−アラビソ７／／ヘキソフラ
ノシド〔〕 ／実施例１で得られた化合
物〔〕（１．８ｇ）のジクロルメタン溶液（２５ｍ１）
に、ＮａＯＣＨ３（１２０ηのＮａを５ｍ１のメタノー
ルに溶かして調製したもの）を加え、室温で２時間攪拌
した。The solvent was distilled off under reduced pressure to obtain a syrupy substance, which was subjected to silica gel column chromatography. C
When eluted with HCl3CH3OH (20:1 v/v),
A syrupy compound [] (1.59, yield 85%) was obtained. Example 2 Methyl 5,6-anthitro 2,3-dideoxy-2-
C-cyanomethyl-β-D-arabiso 7//hexofuranoside [] / Dichloromethane solution (25 ml) of the compound [] (1.8 g) obtained in Example 1
To this, NaOCH3 (prepared by dissolving 120 η of Na in 5 ml of methanol) was added, and the mixture was stirred at room temperature for 2 hours.
冷飽和ＮＨ４Ｃｌ溶液（１０ｍ１）で洗浄し、ＭｇＳＯ
４で乾燥した後、減圧下で溶媒を留去すると、シロツプ
状物質を得た。これを、シリカゲルカラムクロマトグラ
フイ一に付し、ベンゼン一酢酸エチル（２０：１ｖ／ｖ
）で溶出すると、シロツプ状の化合物（Ｔｆｆ）（９１
０ｍｆｉ１定量的）が得られた。Wash with cold saturated NH4Cl solution (10 ml) and MgSO
After drying at step 4, the solvent was distilled off under reduced pressure to obtain a syrup-like substance. This was subjected to silica gel column chromatography and benzene monoethyl acetate (20:1v/v
), a syrupy compound (Tff) (91
0 mfi1 quantitative) was obtained.
実施例 ３
１（Ｓ）−２−オキソ一３（Ｒ）−メトキシ−４（Ｒ）
，５（Ｓ）−シアノ−６（Ｒ）−ヒドロキシメチルビシ
クロ〔２，２，１〕ヘプタン〔〕ヘキサメチルジシラザ
ン（３２３ｍｇ）の乾燥エーテル（１０ｍ０溶液に、窒
素雰囲気中で、ブチルリチウム（１．５ｍ１１１５％ヘ
キサン溶液）を加えた。Example 3 1(S)-2-oxo-3(R)-methoxy-4(R)
,5(S)-cyano-6(R)-hydroxymethylbicyclo[2,2,1]heptane[]hexamethyldisilazane (323 mg) in dry ether (10 ml) in a nitrogen atmosphere was added with butyllithium (1 .5ml of 115% hexane solution) was added.
混合物を３０分間還流した後、溶媒を減圧残つた固体を
乾燥テトラヒドロフランに溶解した。After the mixture was refluxed for 30 minutes, the solvent was vacuumed and the remaining solid was dissolved in dry tetrahydrofuran.
、この溶液に、実施例２で。, to this solution in Example 2.
７，Ｊ０＊＝：ニニ糊ｊ″゜゜゜゛
この混合物を、室温で１時間攪拌した後、冷飽和ＮＨ４
Ｃｌ溶液（２０ｍ０に注ぎ、次いでＣＨ２Ｃｌ２（１０
ｍ１）で３回抽出した。7, J0*=: Nini paste j″゜゜゜゛This mixture was stirred at room temperature for 1 hour, then cooled with saturated NH4
Cl solution (20 mO), then CH2Cl2 (10
m1) was extracted three times.
抽出物を、冷飽和ＮＨ４Ｃｌ溶液で洗浄し、次いでＭｇ
ＳＯ４で乾燥した。減圧下、溶媒を留去するとシロツプ
状物質（１８０η）が得られ、これをシリカゲル（１０
９）のカラムクロマトグラフイ一に付した。The extract was washed with cold saturated NH4Cl solution and then Mg
Dry with SO4. When the solvent was distilled off under reduced pressure, a syrup-like substance (180η) was obtained, which was mixed with silica gel (10
9) was subjected to column chromatography.
Claims (1)
で処理して、構造式：▲数式、化学式、表等があります
▼ で表わされる化合物を得ることを特徴とする光学活性シ
クロペンタン化合物の製造法。 ３ 構造式： ▲数式、化学式、表等があります▼ （ただし、Ｔｓは、トシル基を示す。 ）で表わされる化合物を、アルカリで処理して、構造式
：▲数式、化学式、表等があります▼ で表わされる化合物を得、該化合物を、リチオヘキサメ
チルジシラジドで処理して、構造式：▲数式、化学式、
表等があります▼で表わされる化合物を得ることを特徴
とする光学活性シクロペンタン化合物の製造法。 ４ 構造式： ▲数式、化学式、表等があります▼ で表わされる化合物を、トシル化して、構造式：▲数式
、化学式、表等があります▼（ただし、Ｔｓは、トシル
基を示す。 ）で表わされる化合物を得、該化合物をアルカリで処理
して構造式：▲数式、化学式、表等があります▼ で表わされる化合物を得、該化合物を、リチオヘキサメ
チルジシラジドで処理して、構造式：▲数式、化学式、
表等があります▼で表わされる化合物を得ることを特徴
とする光学活性シクロペンタン化合物の製造法。[Claims] 1. An optically active cyclopentane compound represented by the following structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 2 Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Treat the compound represented by lithiohexamethyldisilazide to obtain the compound represented by the structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing an optically active cyclopentane compound, characterized by: 3 Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Ts indicates a tosyl group.) When the compound represented by is treated with an alkali, the structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc. A compound represented by ▼ is obtained, and the compound is treated with lithiohexamethyldisilazide to form the structural formula: ▲mathematical formula, chemical formula,
A method for producing an optically active cyclopentane compound, which is characterized by obtaining a compound represented by ▼. 4 Structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ By tosylating the compound represented by, the structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Ts indicates a tosyl group.) A compound represented by the formula is obtained, and the compound is treated with an alkali to obtain a compound represented by the structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Formula: ▲Mathematical formula, chemical formula,
A method for producing an optically active cyclopentane compound, which is characterized by obtaining a compound represented by ▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1392980A JPS5927345B2 (en) | 1980-02-07 | 1980-02-07 | Optically active cyclopentane compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1392980A JPS5927345B2 (en) | 1980-02-07 | 1980-02-07 | Optically active cyclopentane compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56110685A JPS56110685A (en) | 1981-09-01 |
| JPS5927345B2 true JPS5927345B2 (en) | 1984-07-05 |
Family
ID=11846865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1392980A Expired JPS5927345B2 (en) | 1980-02-07 | 1980-02-07 | Optically active cyclopentane compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5927345B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3830878A1 (en) * | 1988-09-07 | 1990-03-08 | Schering Ag | 2-OXA-BICYCLO (2.2.1) HEPTANE DERIVATIVES AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS |
-
1980
- 1980-02-07 JP JP1392980A patent/JPS5927345B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56110685A (en) | 1981-09-01 |
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