Enantioselective Synthesis of α-Quaternary Mannich Adducts by Palladium-Catalyzed Allylic Alkylation: Total Synthesis of (+)-Sibirinine

被引：60
作者：
Numajiri, Yoshitaka [1 ]
Pritchett, Beau P. [1 ]
Chiyoda, Koji [1 ]
Stoltz, Brian M. [1 ]
机构：
[1] CALTECH, Div Chem & Chem Engn, Warren & Katharine Schlinger Lab Chem & Chem Engn, Pasadena, CA 91125 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 03期
基金：
日本学术振兴会;
关键词：
DECARBOXYLATIVE ALLYLATION; ASYMMETRIC-SYNTHESIS; FORMAL SYNTHESIS; BETA-KETOESTERS; KETONES; IMINES; AMINOMETHYLATION; (+)-ISONITRAMINE; ISONITRAMINE; CARBAZOLONES;
D O I：
10.1021/ja512124c
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A catalytic enantioselective method for the synthesis of alpha-quaternary Mannich-type products is reported. The two-step sequence of (1) Mannich reaction followed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effect access asymmetric Mannich-type products of thermodynamic enolates of substrates possessing additional enolizable positions and acidic protons. Palladium-catalyzed decarboxylative allylic alkylation enables the enantioselective synthesis of five-, six-, and seven-membered ketone, lactam, and other heterocyclic systems. The mild reaction conditions are notable given the acidic free NH groups and high functional group tolerance in each of the substrates. The utility of this method is highlighted in the first total synthesis of (+)-sibirinine.
引用
收藏
页码：1040 / 1043
页数：4
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