A Mixed-Ligand Chiral Rhodium(II) Catalyst Enables the Enantioselective Total Synthesis of PiperarborenineB

被引：78

作者：

Panish, Robert A. ^{[1
]}

Chintala, Srinivasa R. ^{[1
]}

Fox, Joseph M. ^{[1
]}

机构：

[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 16期

基金：

美国国家科学基金会;

关键词：

bicyclobutane; chiral rhodium catalyst; homoconjugate addition; piperarborenine B; strained molecules; CYCLOBUTANOID AMIDES; STRUCTURAL REVISION; ARYLATION; ALKYLATION; PHOTOCYCLOADDITION; FUNCTIONALIZATION; INCARVILLATEINE; ACTIVATION; ALCOHOLS; SP(2);

D O I：

10.1002/anie.201600766

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel, mixed-ligand chiral rhodium(II) catalyst, Rh-2(S-NTTL)(3)(dCPA), has enabled the first enantioselective total synthesis of the natural product piperarborenine B. A crystal structure of Rh-2(S-NTTL)(3)(dCPA) reveals a chiral crown conformation with a bulky dicyclohexylphenyl acetate ligand and three N-naphthalimido groups oriented on the same face of the catalyst. The natural product was prepared on large scale using rhodium-catalyzed bicyclobutanation/ copper-catalyzed homoconjugate addition chemistry in the key step. The route proceeds in ten steps with an 8% overall yield and 92% ee.

引用

页码：4983 / 4987

页数：5

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