新型双齿P-手性二氨基氧化膦前配体的合成：在钯催化的不对称烯丙基取代反应中的应用

Synthesis of novel bidentate P-chiral diaminophosphine oxide preligands: application to Pd-catalyzed asymmetric allylic substitution reactions.

作者信息

Harada Teisuke, Nemoto Tetsuhiro, Jin Long, Hamada Yasumasa

机构信息

Graduate School of Pharmaceutical Sciences, Chiba University, Chiba, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2011;59(3):412-5. doi: 10.1248/cpb.59.412.

DOI:10.1248/cpb.59.412

PMID:21372429

Abstract

We developed a novel (S)-L-phenylalanine derived-bidentate chiral diaminophosphine oxide (DIAPHOX) preligand (S,S(P))-9b, which was successfully applied to Pd-catalyzed asymmetric allylic alkylation and amination. Using the Pd-(S,S(P))-9b catalyst system, asymmetric allylic alkylation and amination proceeded very smoothly, affording the corresponding products in excellent yield with high enantiomeric excess. It is noteworthy that both enantiomers were accessible with high enantiomeric purity using the structurally related DIAPHOX preligands (S,S(P))-9b and a monodentate chiral diaminophosphine oxide preligand (S,R(P))-10a, both of which can be prepared from a single chiral source, (S)-L-phenylalanine.

摘要

我们开发了一种新型的由（S）-L-苯丙氨酸衍生的双齿手性二氨基氧化膦（DIAPHOX）前体配体（S,S(P)）-9b，它已成功应用于钯催化的不对称烯丙基烷基化和胺化反应。使用钯-（S,S(P)）-9b催化剂体系，不对称烯丙基烷基化和胺化反应进行得非常顺利，以优异的产率和高对映体过量得到相应产物。值得注意的是，使用结构相关的DIAPHOX前体配体（S,S(P)）-9b和单齿手性二氨基氧化膦前体配体（S,R(P)）-10a都可以以高对映体纯度得到两种对映体，这两种配体都可以从单一手性源（S）-L-苯丙氨酸制备。