Organocatalytic asymmetric reactions using (S)-homoproline

使用 (S)-高脯氨酸的有机催化不对称反应

• 批准号: 17550028
• 负责人: ORIYAMA Takeshi
• 金额: $ 2.37万
• 依托单位: Ibaraki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550028/
• 关键词: Organocatalyst; Proline; Michael addition; Homoproline; Thiol; Solvent-free; Asymmetric reaction; プロリン系有機溶媒; 不斉1,4-付加反応; ヒドロキシプロリン; 疎水性; 水中; (S)-ホモプロリン; 不斉マイケル付加反応

Recently, proline or its derivatives-catalyzed asymmetric carbon-carbon bond-forming reactions such as aldol reaction, the Michael addition, and Mannich-type reaction were studied intensively by many organic chemists. Excellent enantioselectivity was attained in various types of organocatalytic asymmetric reactions, but the Michael addition has some serious limitations. For example, there are scattered examples over 90% ee, and substrate generality is not so high. On the other hand, we have developed a novel asymmetric Michael addition reaction of ketone to b-nitrostyrene and its derivatives using (5)-homoproline as a chiral organocatalyst. The reaction was performed in a highly diastereoselective and enantioselective manner over 90% ee. Furthermore, we have developed solvent-free organocatalytic asymmetric conjugate addition of thiols to a, b-unsaturated aldehydes. In the presence of well-designed organocatalyst, the reaction proceeds without any organic solvents, giving the corresponding chiral sulfides in almost enantiomerically pure form (up to 99% ee). Moreover, b, b-disubstituted a, b-unsaturated aldehydes also reacted with phenylmethanethiol. This method is environment-friendly, economical, and convenient.

近年来，脯氨酸或其衍生物催化的羟醛反应、迈克尔加成反应、曼尼希型反应等不对称碳-碳成键反应得到了许多有机化学家的深入研究。在各种类型的有机催化不对称反应中都获得了优异的对映选择性，但迈克尔加成有一些严重的局限性。例如，有超过90% ee的零星例子，并且基材通用性不是那么高。另一方面，我们开发了一种新型的酮与b-硝基苯乙烯及其衍生物的不对称迈克尔加成反应，使用(5)-高脯氨酸作为手性有机催化剂。该反应以超过 90% ee 的高度非对映选择性和对映选择性方式进行。此外，我们还开发了硫醇与a，b-不饱和醛的无溶剂有机催化不对称共轭加成。在精心设计的有机催化剂存在下，反应无需任何有机溶剂即可进行，得到几乎对映体纯形式的相应手性硫化物（高达 99% ee）。此外，b，b-二取代的a，b-不饱和醛也与苯基甲硫醇反应。该方法环保、经济、方便。

项目成果

Solvent-free organocatalytic asymmetric conjugate addition of thiols to α,β-unsaturated aldehydes

• DOI: 10.1246/cl.2007.550
• 发表时间: 2007-04-05
• 期刊: CHEMISTRY LETTERS
• 影响因子: 1.6
• 作者: Ishino, Takeru;Oriyama, Takeshi
• 通讯作者: Oriyama, Takeshi

Organocatalytic kinetic resolution of racemic primary alcohols using a chiral 1,2-diamine derived from (S)-proline

• DOI: 10.1016/j.tetasy.2005.01.034
• 发表时间: 2005-03-21
• 期刊: TETRAHEDRON-ASYMMETRY
• 作者: Terakado, D;Koutaka, H;Oriyama, T
• 通讯作者: Oriyama, T

CATALYTIC ASYMMETRIC ACYLATION OF ALCOHOLS USING CHIRAL 1,2-DIAMINE DERIVED FROM (S)-PROLINE : (1S,2S)-trans-1-BENZOYLOXY-2-BR OMOCYCLOHEXANE

使用 (S)-脯氨酸衍生的手性 1,2-二胺催化醇的不对称酰化：(1S,2S)-trans-1-苯甲酰氧基-2-BR 四环己烷

• 发表时间: 2006
• 期刊: ORGANIC SYNTHESES Vol. 83
• 作者: D.Terakado;T.Oriyama
• 通讯作者: T.Oriyama