Preparation and Utilization of Chiral alpha-and beta-Hydroxyacetylenes

手性α-和β-羟基乙炔的制备和应用

• 批准号: 02670941
• 负责人: TAKAHASHI Michiyasu
• 金额: $ 1.47万
• 依托单位: TOHOKU 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: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02670941/
• 关键词: enantiocontrolled synthesis; resolution; enantiocomplementary resolution; lipase; lipase in organic solvent; chiral synthon; vitamin D_3; vincamine; キラル2-メチル-2-シクロペンテノール; キラル2-カルボエトキシ-2-シクロペンテノール; リパーゼ関与不斉分割; 不斉加水分解; エナンチオ相補分割法; キラル合成ブロック; 2

Intending to obtain versatile chiral 2-cyclopentenol building blocks, enzymatic resolution of several 2-substituted 2-cyclopentenol derivatives has been investigated. Having been tested, 2-carbethoxy-2-cyclopentenol has been cleanly resolved by lipase PS under both trans-esterification in organic solvent and deacylation in buffer solution in virtually complete enantiospecific manner in high chemical yields. Owing to characteristic feature of the enzymatic reaction, the reaction occurred at the same stereogenic configuraion which made enantiocomplementary resolution possible.Utilizing the optically pure cyclopentenols thus obtained, efficient syntheses of the key intermediate of 1,25-dihydroxyvitamin D_3 and vincamine have been achieved.

为了获得多功能的手性2-环戊烯醇结构单元，研究了几种2-取代的2-环戊烯醇衍生物的酶促拆分。经过测试，2-乙氧羰基-2-环戊烯醇已干净地拆分脂肪酶PS在两个转酯在有机溶剂中和脱酰在缓冲溶液中，在几乎完全的对映体特异性的方式在高的化学产率。由于酶促反应的特点，反应发生在同一立体构型上，使对映体互补拆分成为可能，利用所得光学纯的环戊烯醇，实现了关键中间体1，25-二羟基维生素D_3和长春胺的高效合成。

项目成果

Seiichi Takano: "Efficient Chiral Route to a Key Building Block of 1,25-Dihydroxyvitamin D_3 via Lipase Mediated Resolution" Synlett. 410-412 (1992)

Seiichi Takano：“通过脂肪酶介导的拆分，实现 1,25-二羟基维生素 D_3 关键构建模块的有效手性路线”Synlett。

Seiichi Takano: "Efficient Chiral Route to a Key Building Block of 1,25-Dihydroxy-vitamin D_3 via Lipase Mediated Resolution" Synlett. 410-412 (1992)

Seiichi Takano：“通过脂肪酶介导的拆分，实现 1,25-二羟基维生素 D_3 关键构建模块的有效手性路线”Synlett。

Seiichi Takano: "Enantiocomplementary Synthesis of Functionalized Cycloalkenol Building Blocks Using Lipase" Tetrahedron: Asymmetry. 3. 837-840 (1992)

Seiichi Takano：“使用脂肪酶对功能化环烯醇构建块进行对映互补合成”四面体：不对称性。

Seiichi Takano: "Enantioconvergent Route to Vincamine" 投稿準備中.

Seiichi Takano：“长春胺的对映收敛路线”准备提交。

Seiichi Takano: "Practical Preparation of Optically Active OーBenzylーglycidol from Optically Active Epichlorohydirn" Heterocycles. 31. 1715-1719 (1990)

Seiichi Takano：“从光学活性环氧氯丙烷实际制备光学活性 O-苄基缩水甘油”杂环。 31. 1715-1719 (1990)