Efficient Synthesis of Sulfur-functionalized Cycloalkanol as a Chiral Synthon.

作为手性合成子的硫官能化环烷醇的有效合成。

• 批准号: 03453027
• 负责人: FUJISAWA Tamotsu
• 金额: $ 5.31万
• 依托单位: Mie University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453027/
• 关键词: Bakers' Yeast Reduction; Sulfur-containing Chiral Synthon; Stereoselective Reduction; Prostaglandin Intermediate; Aggregation Pheromone; Chiral Cycloalkanol; Tetrahydrothiopyran; Ranberg-Baecklund Reaction; 光学活性β-ケトール; サイトフイルアー; 光学活性シクロアロカノ-ル

The stereoselective reduction of sulfur-functionalized cyclic ketones with bakers' yeast leading to cyclic carbinols bearing two adjacent chiral centers and the subsequent transformations into biologically interesting compounds were studied. The bakers' yeast reduction of 2-phenylthiocyclopentanone, 2-phenylthiocyclohexanone, and 2-phenylthio-2-cyclopentenones proceeds well to give optically pure (1S,2R)-1-phenylthio-cycloalkanols. Furthermore, 4-oxo-3-tetrahydrothiopyranylacetates were reduced with bakers' yeast to give optically pure (3S,4S)-4-hydroxy-3-tetrahydrothiopyranylacetate, which was converted into an optically pure prostaglandin intermediate. The bakers' yeast reduction of 3-acyltetrahydrothiopyran-4-ones gave (3S,4S)-3-acyl-4-hydroxytetrahydro-thiopyrane with high regio-and enantioselectivity. In particular, the reduction of 3-propionyltetrahydrothiopyran-4- one took place regioselectively to give a single (3R,4S)-isomer in optically pure form in good yield, and the subsequent desulfurization by Raney-Ni gave the insect aggregation pheromone, (-)-(4R,5S)-Sitophilure with high optical purity.

研究了用面包酵母立体选择性还原硫官能化环酮，产生带有两个相邻手性中心的环甲醇，以及随后转化为具有生物学意义的化合物。 2-苯硫基环戊酮、2-苯硫基环己酮和2-苯硫基-2-环戊烯酮的面包酵母还原反应进行得很好，得到光学纯的(1S,2R)-1-苯硫基-环烷醇。此外，用面包酵母还原4-氧代-3-四氢噻喃基乙酸酯，得到光学纯的(3S,4S)-4-羟基-3-四氢噻喃基乙酸酯，将其转化为光学纯的前列腺素中间体。 3-酰基四氢噻喃-4-酮的面包酵母还原得到具有高区域选择性和对映选择性的(3S,4S)-3-酰基-4-羟基四氢-噻喃。特别是，3-丙酰四氢噻喃-4-1发生区域选择性还原，以良好的收率得到光学纯形式的单一(3R,4S)-异构体，随后通过Raney-Ni脱硫得到具有高光学纯度的昆虫聚集信息素，(-)-(4R,5S)-Sitophilure。

项目成果

T.Fujisawa: "A Short Synthesis of(-)-(4R,5S)-Sitophilure using the Regio-and Stereoselective Reduction of 3-Acyltetrahydrothiopyran-4-ones with Bakers'Yeast" Tetrahedron Lett.33. 5567-5570 (1992)

T.Fujisawa：“使用面包酵母对 3-酰基四氢噻喃-4-酮进行区域选择性和立体选择性还原来合成 (-)-(4R,5S)-Sitophilure”四面体 Lett.33。

T.Fujisawa,K.Yamanaka,B.I.Mobele,M.Shimizu: "Highly Enantio-and Diastereo-selective Reduction of Sulfur-functionalized Cyclic Ketones with Bakers' Yeast" Tetrahedron Lett.32. 399-400 (1991)

T.Fujisawa、K.Yamanaka、B.I.Mobele、M.Shimizu：“用面包酵母对硫官能化环酮进行高度对映和非对映选择性还原”四面体 Lett.32。

T.Fujusawa: "Highly Enantio- and Diastereo-selective Reduction of Sulfur-functionalized Cyclic Ketones with Bakers'Yeast" Tetrahedron Lett.32. 399-400 (1991)

T.Fujusawa：“用面包酵母对硫官能化环酮进行高度对映和非对映选择性还原”Tetrahedron Lett.32。

T.Fujisawa: "Enantioselective Reduction of 4-Oxo-3-tetrahydrothiopyranylacetate with Bakers'Yeast," Tetrahedron Lett.32. 7055-7058 (1991)

T.Fujisawa：“用面包酵母对 4-Oxo-3-四氢噻喃基乙酸酯进行对映选择性还原”，Tetrahedron Lett.32。

T.Fujusawa: "A Short Synthesis of (_-)_-(4R,5S)_- Sitophilure using the Regio- and stereoselective Reduction of 3_-Acyltetrahydrothipyran_-4_-ones with Bakers'Yeast" Tetrahedron Lett.33. 5567-5570 (1992)

T.Fujusawa：“使用面包酵母对 3_-酰基四氢噻喃_-4_-酮进行区域选择性和立体选择性还原来合成 (_-)_-(4R,5S)_- Sitophilure”四面体 Lett.33。