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，脯氨酸及其衍生物催化的不对称碳-碳键形成反应，如羟醛缩合反应、Michael加成反应、Mannich反应等受到了有机化学家的广泛关注。有机催化的不对称反应具有很好的对映选择性，但Michael加成反应存在严重的局限性。例如，有分散的例子超过90%ee，和基板的通用性不是很高。另一方面，我们发展了一种新的以（5）-高脯氨酸为手性催化剂的酮与b-硝基苯乙烯及其衍生物的不对称Michael加成反应。该反应是在一个高度的非对映选择性和对映选择性的方式超过90%ee。此外，我们已经开发了无溶剂的有机催化的不对称共轭加成硫醇的a，b-不饱和醛。在精心设计的有机催化剂的存在下，该反应在没有任何有机溶剂的情况下进行，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-不饱和醛也与苯甲烷乙炔反应。该方法环保、经济、方便。

项目成果

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 a Chiral 1,2‐Diamine Derived from (S)‐Proline: (1S,2S)‐trans‐1‐Benzoyloxy‐2‐bromocyclohexane

• DOI: 10.1002/0471264229.os083.11
• 发表时间: 2006-04
• 期刊: Organic Syntheses
• 影响因子: 0.7
• 作者: Dai Terakado;T. Oriyama*

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

「有機分子触媒の新展開」

《有机分子催化剂的新进展》

• 发表时间: 2006
• 作者: Sasaki K;Matsumura S;Toshima K;柴崎正勝(監修)
• 通讯作者: 柴崎正勝(監修)

Highly Enantioselective (S)-Homoproline-catalyzed Michael Addition Reactions of Ketones to β-Nitrostyrenes

• DOI: 10.1246/cl.2005.962
• 发表时间: 2005-06
• 期刊: Chemistry Letters
• 影响因子: 1.6
• 作者: Dai Terakado;M. Takano;T. Oriyama*