New Method for Asymmetric Synthesis by Using Chiral Bases

利用手性碱基进行不对称合成的新方法

• 批准号: 08557122
• 负责人: KOGA Kenji
• 金额: $ 8万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08557122/
• 关键词: lithium enolate; asymmetric synthesis; catalytic asymmetric synthesis; deprotonation; alkylation; protonation; Michael reaction; chiral amine; 四級不斉炭素; エナンチオ選択的; キラル塩基; キラルリチウムアミド; 脱プロトン化; プロトン化

Enantioselctive synthesis and reactions of enolate ions are one of the important area in modern synthetic chemistry. The aim of this project is the design and synthesis of multidentate-type chiral lithium amides and the corresponding chiral amines, their applications to the enantioselective synthesis of chiral lithium enolates and to the enantioselective reactions of prochiral lithium enolates, and the development of these reactions to highly catalytic systems. We obtained the following results through this project.(1) The combination of a catalytic amount of a chiral amine and a stoichiometric amount of an achiral lithium amide has realized catalytic asymmetric deprotonation reactions of prochiral ketones.(2) The new C_2 symmetric chiral tetraamine has been found to be an excellent ligand for catalytic asymmetric alkylation of lithium enolates derived from alpha, alpha-disubstituted ketones.(3) Catalytic asymmetric protonation of prochiral ketones has been realized by using a catalytic amount of chiral tetraamine and a proton source which is hardly soluble in the solvent used.(4) Enantioselective Michael reactions of acyclic ketones have been realized by using a chiral tetraamine.

烯醇离子的对映选择性合成和反应是现代合成化学的重要领域之一。该项目的目的是设计和合成多齿型手性氨基锂和相应的手性胺，它们在手性烯醇锂对映选择性合成和前手性烯醇锂对映选择性反应中的应用，以及将这些反应开发为高催化体系。通过该项目，我们获得了以下成果：(1)催化量的手性胺与化学计量的非手性氨基锂的组合实现了前手性酮的催化不对称去质子化反应。(2)新的C_2对称手性四胺被发现是催化锂不对称烷基化的优异配体 (3)利用催化量的手性四胺和难溶于所用溶剂的质子源，实现了前手性酮的催化不对称质子化。(4)利用手性四胺，实现了无环酮的对映选择性迈克尔反应。

项目成果

Kazumasa Aoki: "Enantio Selective Deprotonation of 4-tert-Butylcyclohexanone by Fluorine-Containing Chiral Lithium Amides Derived from α-Phenethylamine." Tetrahedron Letters. 38. 2505-2506 (1997)

Kazumasa Aoki：“由 α-苯乙胺衍生的含氟手性锂酰胺对 4-叔丁基环己酮进行对映选择性去质子化。”38。2505-2506 (1997)

K.Yasuda: "Enantioselective Michael Reaction of Ketone Lithium Enolates Using Chiral Amine Ligand." Tetrahedron Lett.37. 6343-6 (1996)

K.Yasuda：“使用手性胺配体进行酮锂烯醇化物的对映选择性迈克尔反应。”

K.Sugasawa: "Solution structures of a Monodentate Chiral Lithium Amide in the Presence of Lithium Halide." Tetrahedron Lett.37. 7377-80 (1996)

K.Sugasawa：“卤化锂存在下单齿手性氨基锂的溶液结构。”

H.Chatani: "Chiral Bidentate Lithium Amides Having a Chiral Amide Nitrogen for Enantioselective Deprotonation of 4-tert-Butylcyclohexanone." Heterocycles. 46. 53-6 (1997)

H.Chatani：“具有手性酰胺氮的手性双齿锂酰胺，用于 4-叔丁基环己酮的对映选择性去质子化。”

K.Aoki.: "Enantioselective deprotonation of 4-tert-butylcyclo hexanone by pluorine-cotaining chiral lithium amides dereved fromt α-phenethylamine." Tetrahedron Lett.38. 2505-2506 (1997)

K.Aoki.：“由 α-苯乙胺衍生的含氟手性氨基锂对 4-叔丁基环己酮进行对映选择性去质子化。”38 (1997)。