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钯催化醇的烷氧羰基化反应合成具有α-季碳中心的环丁烷羧酸酯

Palladium-Catalyzed Alkoxycarbonylation of Alcohols for the Synthesis of Cyclobutanecarboxylates with α-Quaternary Carbon Centers.

作者信息

Liu Yu-Kun, Gu Xing-Wei, Wu Xiao-Feng

机构信息

Leibniz-Institut für Katalyse e. V., Albert-Einstein-Straße 29a, 18059 Rostock, Germany.

Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.

出版信息

Org Lett. 2025 Feb 7;27(5):1316-1321. doi: 10.1021/acs.orglett.5c00087. Epub 2025 Jan 27.

DOI:10.1021/acs.orglett.5c00087
PMID:39869049
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11811996/
Abstract

A palladium-catalyzed alkoxycarbonylation with two different alcohols for the synthesis of cyclobutanecarboxylates bearing an α-quaternary carbon center is presented. The reaction utilizes readily accessible starting materials, tolerates a broad scope of functional groups, and provides a straightforward and efficient approach for the synthesis of a diverse array of cyclobutanecarboxylates bearing an α-quaternary carbon. Meanwhile, this strategy effectively prevents the transition-metal-catalyzed ring-opening of cyclobutanols, preserves the cyclobutane framework, and affords 1,1-disubstituted cyclobutanecarboxylates in high yields with excellent regioisomeric ratios.

摘要

本文报道了一种钯催化的用两种不同醇进行的烷氧基羰基化反应,用于合成带有α-季碳中心的环丁烷羧酸酯。该反应使用易于获得的起始原料,能耐受多种官能团,并为合成各种带有α-季碳的环丁烷羧酸酯提供了一种直接且高效的方法。同时,该策略有效地防止了环丁醇的过渡金属催化开环,保留了环丁烷骨架,并以高收率和优异的区域异构体比例得到1,1-二取代的环丁烷羧酸酯。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/d3b41f3b17cc/ol5c00087_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/f7220d16666a/ol5c00087_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/0ebddece3b7d/ol5c00087_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/25e32dca7b3d/ol5c00087_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/619a061e66d0/ol5c00087_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/d3b41f3b17cc/ol5c00087_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/f7220d16666a/ol5c00087_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/0ebddece3b7d/ol5c00087_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/25e32dca7b3d/ol5c00087_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/619a061e66d0/ol5c00087_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/39b2/11811996/d3b41f3b17cc/ol5c00087_0005.jpg

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本文引用的文献

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Photochemical α-selective radical ring-opening reactions of 1,3-disubstituted acyl bicyclobutanes with alkyl halides: modular access to functionalized cyclobutenes.1,3-二取代酰基双环丁烷与卤代烷的光化学α-选择性自由基开环反应:功能化环丁烯的模块化合成方法
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