钯催化炔丙醇与 CO 和芳基卤化物的芳基羧化反应：制备功能化的α-烷基烯丙基环碳酸酯。

Palladium-Catalyzed Arylcarboxylation of Propargylic Alcohols with CO and Aryl Halides: Access to Functionalized α-Alkylidene Cyclic Carbonates.

机构信息

School of Petrochemical Engineering, Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, and Institute for Natural and Synthetic Organic Chemistry, Changzhou University , Changzhou 213164, P. R. China.

出版信息

Org Lett. 2017 Mar 3;19(5):1088-1091. doi: 10.1021/acs.orglett.7b00111. Epub 2017 Feb 23.

DOI:10.1021/acs.orglett.7b00111

PMID:28229599

Abstract

A palladium-catalyzed, three-component reaction between propargylic alcohols, CO, and aryl halides was developed whereby a sequential carboxylation, trans-oxopalladation of the C≡C bond by an ArPdX species, and a reductive elimination procedure afforded a series of functionalized α-alkylidene cyclic carbonates in moderate to excellent yields. Notably, the configuration of these tetrasubstituted olefins was dominated by the trans-oxopalladation step where the aryl group derived from ArX is located trans to the oxygen attached in the double bond. This protocol features simultaneous formation of four novel bonds in a one-pot reaction, representing an efficient method for incorporation of CO into heterocycles.

摘要

钯催化的丙炔醇、CO 和芳基卤化物的三组分反应，通过 ArPdX 物种对 C≡C 键的顺式氧化钯化、以及还原消除步骤，以中等至优异的收率得到一系列官能化的α-亚烷基环状碳酸酯。值得注意的是，这些四取代烯烃的构型主要由顺式氧化钯化步骤决定，其中来自 ArX 的芳基基团位于双键中氧原子的反式位置。该方案在一锅反应中同时形成四个新键，代表了将 CO 掺入杂环中的有效方法。