通过催化 Meyer-Schuster 重排反应对α,α'-二乙烯基酮的烯丙基化反应。

Olefination of α,α'-divinyl ketones through catalytic Meyer-Schuster rearrangement.

机构信息

Department of Chemistry, University of Alberta, E3-43 Gunning-Lemieux Chemistry Centre, Edmonton, AB T6G 2G2, Canada.

出版信息

J Org Chem. 2011 Jan 7;76(1):50-6. doi: 10.1021/jo101497f. Epub 2010 Nov 24.

Abstract

The direct olefination of 1,4-dien-3-ones remains a synthetic challenge. A two-step protocol, employing acetylide addition followed by catalytic Meyer-Schuster rearrangement has been developed for the olefination of 1,4-pentadien-3-ones to afford [3]dendralenes. Many of the traditional methods for the Meyer-Schuster rearrangement of alkynyl carbinols are not suitable with these highly unsaturated substrates because of their acid sensitivity. Unexpected reactivity during attempted rearrangement, including Nazarov-type electrocyclizations, is presented, along with conditions to promote the Meyer-Schuster rearrangement of ethoxyacetylene adducts using catalytic VO(acac)(2).

摘要

1,4-二烯-3-酮的直接烯烃化仍然是一个合成挑战。开发了一种两步法方案，采用炔化物加成，然后催化 Meyer-Schuster 重排，将 1,4-戊二烯-3-酮烯烃化得到[3]倍半萜烯。由于这些高度不饱和的底物对酸敏感，许多传统的炔基甲醇 Meyer-Schuster 重排方法不适用。在尝试重排过程中出现了意想不到的反应性，包括 Nazarov 型电环化，以及使用催化 VO(acac)(2)促进乙氧基乙炔加合物的 Meyer-Schuster 重排的条件。