Development of Chiral Ligand Based on Double Asymmetric Induction and Application to Catalytic Reaction.

基于双不对称诱导的手性配体的开发及其在催化反应中的应用。

• 批准号: 08455433
• 负责人: SUZUKI Akira
• 金额: $ 3.58万
• 依托单位: KURASHIKI UNIVERSITY OF SCIENCE AND THE ARTS
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455433/
• 关键词: PALLADIUM CATALYST; ASYMMETRIC REACTION; CHIRAL LIGAND; 不斉誘起; 不斉触媒反応; 重複不斉反応; 有機金属触媒

The envisioned ligand is monodentate phosphine ligand for palladium catalyst. The new chiral ligand was designed based on the double asymmetric induction methodology which is well known in a usual asymmetric reaction. Thus, the combination of axial chirality and chiral auxiliary constitutes the backbone of the chiral ligand. Initially, the axially chiral fragment was binaphthalene framework, because the skeleton has been proved to exhibit most efficient induction ability. As an another chiral auxiliary, oxazohdine and acetal structures were selected. Diphenylphosphino group and chiral auxiliary were planned to be put on 2 and 2' positions on the binaphthalene framework. Although the most desired ligand could not be synthesized in spite of intensive trials, another ligand was prepared and tested in several palladium catalyzed reactions. Unfortunately, the high asymmetric induction was not observed so far under the typical reaction conditions in each catalyzed reaction. However, this concept is believed to be anew direction to obtain more efficient chiral ligand.

设想的配体是用于钯催化剂的单齿膦配体。新的手性配体是基于双重不对称诱导方法设计的，这种方法在常见的不对称反应中是众所周知的。因此，轴向手性和手性助剂的组合构成了手性配体的主干。最初，轴向手性片段是联苯骨架，因为骨架已被证明具有最有效的诱导能力。作为另一种手性助剂，选择了恶唑烷和缩醛结构。二苯基膦基团和手性助剂被计划放置在联苯骨架的2‘和2’位。尽管经过密集的试验仍未能合成出最理想的配体，但还是制备了另一种配体，并在几个钯催化的反应中进行了测试。遗憾的是，到目前为止，在典型的反应条件下，每一种催化反应都没有观察到高度的不对称诱导。然而，这一概念被认为是获得更有效的手性配体的新方向。

项目成果

A. Suzuki: "Haloboration of 1-Alkynes and Its Synthetic Application" Reviews on Heteroatom Chemistry. 17. 271-314 (1997)

A. Suzuki：“1-炔烃的卤硼化及其合成应用”杂原子化学评论。

A.Suzuki: "Cross-Coupling Reactions of Organoboron Compounds with Organic Halidis in “Metal-Catalyzed Cross-coupling Reactions"" Wiley-VCH, 48 (1998)

A.Suzuki：“金属催化交叉偶联反应中有机硼化合物与有机卤化物的交叉偶联反应”Wiley-VCH，48 (1998)

A.Suzuki: "Haloboration, Thioboration, and Diboration Reactions" Proceedings of the 8th Japan-Korea Seminar in Organic Chemistry, Tokyo. 134 (1996)

A.Suzuki：“卤硼化、硫代硼化和二硼化反应”第八届日韩有机化学研讨会论文集，东京。

S.Hara, S.Ishimura, and A.Suzuki: "Cyanuric Fluoride-Induced 1,4-Addition Reaction of Alkenylboronic Acids to alpha, beta-Unsaturated Ketones. Stereoselective Synthesis of gamma, delta-Unsaturated Ketones Having Functionalities." Synlett. 993. (1996)

S.Hara、S.Ishimura 和 A.Suzuki：“三聚氰氟化物诱导的烯基硼酸与 α、β-不饱和酮的 1,4-加成反应。具有功能性的 γ、δ-不饱和酮的立体选择性合成。”

A.Suzuki: "Palladium-Catalyzed Carbonylative Cross-Coupling Reactions" J.Org.Chem. 63. 4726-4731 (1998)

A.Suzuki：“钯催化的羰基交叉偶联反应”J.Org.Chem。