铑（三氟甲磺酸盐）催化的炔丙醇的烷基截获迈耶-舒斯特重排反应用于合成1,2,3,5-四取代戊烷-1,5-二酮

Bi(OTf)-Catalyzed Alkyl-Intercepted Meyer-Schuster Rearrangement of Propargylic Alcohols for the Synthesis of 1,2,3,5-Tetrasubstituted Pentane-1,5-diones.

作者信息

Wang Zhihai, Sun Yuxing, Zhang Qinglin, Pan Wanyong, Li Tiantian, Yin Yan

机构信息

Department of Chemical and Environmental Engineering, Shanghai Institute of Technology, 201418 Shanghai, PR China.

Shanghai Key Laboratory of Chemical Assessment and Sustainability, Tongji University, 1239 Si Ping Road, 200092 Shanghai, PR China.

出版信息

J Org Chem. 2022 Mar 4;87(5):3329-3340. doi: 10.1021/acs.joc.1c02974. Epub 2022 Feb 11.

DOI:10.1021/acs.joc.1c02974

PMID:35147429

Abstract

An alkyl intercepted Meyer-Schuster rearrangement reaction with α,β-unsaturated ketones as the electrophiles was first investigated, which provided a facile method to construct 2-methylene-pentane-1,5-diones. Then the in situ generated 2-methylene-pentane-1,5-diones underwent a Michael addition to give diverse 2-malononitrile methyl substituted pentane-1,5-diones in a one-pot fashion. This transformation was reliable on a gram scale. The high yield, convenient experimental operation, and 100% atom economy made it a valuable method for the construction of 1,2,3,5-tetrasubstituted pentane-1,5-dione derivatives.

摘要

首次研究了烷基与α,β-不饱和酮作为亲电试剂的截获型迈耶-舒斯特重排反应，该反应为构建2-亚甲基戊烷-1,5-二酮提供了一种简便方法。然后原位生成的2-亚甲基戊烷-1,5-二酮进行迈克尔加成，以一锅法得到多种2-丙二腈甲基取代的戊烷-1,5-二酮。这种转化在克级规模上是可靠的。高产率、便捷的实验操作和100%的原子经济性使其成为构建1,2,3,5-四取代戊烷-1,5-二酮衍生物的一种有价值的方法。