生成并捕获环戊烯基金物种：通往多环化合物的四条途径。

Generation and trapping of cyclopentenylidene gold species: four pathways to polycyclic compounds.

机构信息

UPMC Paris 06, Laboratoire de Chimie Organique (UMR CNRS 7611), Institut de Chimie Moléculaire (FR 2769), case 229, 4 place Jussieu, F-75252 Paris cedex 05, France.

出版信息

J Am Chem Soc. 2009 Mar 4;131(8):2993-3006. doi: 10.1021/ja808872u.

DOI:10.1021/ja808872u

PMID:19209868

Abstract

Cyclopentenylidene gold complexes can easily be formed from vinyl allenes through a Nazarov-like mechanism. Such carbenes may transform in four different ways into polycyclic frameworks: electrophilic cyclopropanation, C-H insertion, C-C migration, or proton shift. We have studied the selectivity of these different pathways and used our findings for the expedient preparation of valuable complex molecules. An application to the total synthesis of a natural product, Delta(9(12))-capnellene, is presented. DFT computations were carried out to shed light on the mechanisms.

摘要

环戊烯基金配合物可以很容易地通过类似 Nazarov 的机制从乙烯基丙二烯形成。这些卡宾可以通过四种不同的方式转化为多环框架：亲电环丙烷化、C-H 插入、C-C 迁移或质子迁移。我们研究了这些不同途径的选择性，并利用我们的发现来方便地制备有价值的复杂分子。本文介绍了它们在全合成天然产物 Delta(9(12))-capnellene 中的应用。进行了 DFT 计算以阐明这些反应机制。