Brook Rearrangement as Trigger for Carbene Generation: Synthesis of Stereodefined and Fully Substituted Cyclobutenes

被引：60

作者：

Zhang, Fa-Guang ^{[1
]}

Marek, Ilan ^{[1
]}

机构：

[1] Technion Israel Inst Technol, Schulich Fac Chem, Mallat Family Lab Organ Chem, IL-32000 Haifa, Israel

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 24期

基金：

欧洲研究理事会;

关键词：

ANION RELAY CHEMISTRY; ACYCLIC SYSTEMS; ALPHA-HYDROXYSILANES; STEREOCENTERS; RING EXPANSION; ACYLSILANES; BONDS; FUNCTIONALIZATION; STEREOCHEMISTRY; CYCLOPROPANES;

D O I：

10.1021/jacs.7b04255

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Through a sequence that can be performed in a single vessel, involving regio- and diastereoselective copper-catalyzed carbomagnesiation of cyclopropenes, reaction with acylsilanes, and addition of THE as cosolvent, Brook rearrangement can be triggered to furnish a wide range of cyclobutenes with exceptional diastereoselectivity. Accordingly, stereodefined and highly substituted cyclobutenes with contiguous quaternary carbon centers can be synthesized easily and in high yield. The new strategy constitutes an unprecedented application of Brook rearrangement, one which involves the intermediary of carbene species.

引用

收藏

页码：8364 / 8370

页数：7

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