Asymmetric Synthesis and Use of

不对称合成及用途

• 批准号: 62550634
• 负责人: UTAKA Masanori
• 金额: $ 1.28万
• 依托单位: Okayama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62550634/
• 关键词: Optically active -chloro acids; Optically active 2,4,4-trichlorobutanoic acid; Asymmetric synthesis of both enantiomers; 両鏡像体合成; パン酵母還元; ロイシノピンアナログ; クラウンゴール; 不斉還元; パン酵母; 光学活性α-ハロエステル; α-アミノ酸; α-クロローα, β-不飽和エステル

Asymmetric reduction of (E)- and (Z)-methyl 2-chloro-2-alkenoates by use of fermenting bakers' yeast gave (R)- and (S)-2-chloroalkanoiceacids in 25 92% ee and 98% ee, respectively. The chemical yields were 10 40% for 2-chloropentenoate, 2-chloroheptenoate, but 65 70% for 2,4,4-trichloro- and 2,4,4,4-tetrachlorobutenoates. The substrates were found to be reduced after hydrolysis to the acids. The reactivity and stereoselectivity of the reduction were discussed. The reduction products, (R)- and (S)-2,4,4-trichlorobutanoic acids, were transformed to (S)- and (R)-2-amino-4,4-dichlorobutanoic acids, respectively.In order to prepare a dichloro-substituted leucinopine analog, reaction of 2-amino-4,4-dichlorobutanoic acid with -ketoglutaric acid was investigated.

用发酵面包酵母不对称还原（E）-和（Z）-2-氯-2-烯酸甲酯，分别得到（R）-和（S）-2-氯代链烷酸，其ee值分别为25 92%和98%。2-氯戊烯酸、2-氯庚烯酸的化学产率为10 - 40%，而2，4，4-三氯和2，4，4，4-四氯丁烯酸的化学产率为65 - 70%。发现底物在水解成酸后被还原。讨论了还原反应的反应活性和立体选择性。还原产物（R）-和（S）-2，4，4-三氯丁酸分别转化为（S）-和（R）-2-氨基-4，4-二氯丁酸，并与α-酮基谷氨酸反应制备二氯取代的亮氨酸类似物。

项目成果

Masanori,Utaka; Satoshi,Konishi; Toshiyasu,Okubo; Sadao,Tsuboi; Akira,Takeda: "A facile Synthesis of Optically Pure L-Armentomycin and Its D-Isomer. Highly Enantioselective Reduction of the C-C Double Bond of Methyl (E)- and (Z)-2,4,4-Trichloro-2-butenoat

雅德正德；

Masanori Utaka;Satoshi Konishi;Toshiyasu Okubo;Sadao Tsuboi;Akitra Takeda: Tetrahedron Letters. 28. 1447-1450 (1987)

歌正则；小西智；大久保敏康；坪井贞夫；武田秋：四面体字母。

Masanori Utaka;Satoshi Konishi;Toshiyasu Okubo;Sadao Tsuboi;Akira Takeda: Tetrahedron Letters. 28. 1447-1450 (1987)

歌正则；小西智；大久保敏康；坪井贞夫；武田晃：四面体字母。

Masanori Utaka;Satoshi Konishi;Ami Mizuoka;Toshiyasu Okubo;Takashi Sakai;Sadao Tsuboi;Akira Takeda: Journal of Organic Chemistry.

Masanori Utaka;Satoshi Konishi;Ami Mizuoka;Toshiyasu Okubo;Takashi Sakai;Sadao Tsuboi;Akira Takeda：有机化学杂志。

Masanori,Utaka; Hiroshi,Matsubara; Hisashi,Watabu; Takashi,Sakai; Sadao,Tsuboi: "Separation and Characterization of Four Diastereomers of Leucinopine" Journal of Organic Chemistry.

雅德正德；