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钯催化羰基化合物与氯代芳基三氟甲磺酸酯在C-Cl位点进行化学选择性直接α-芳基化反应。

Palladium-catalyzed chemoselective direct α-arylation of carbonyl compounds with chloroaryl triflates at the C-Cl site.

作者信息

Chen Zicong, Gu Changxue, Yuen On Ying, So Chau Ming

机构信息

State Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University Kowloon Hong Kong SAR China

The Hong Kong Polytechnic University Shenzhen Research Institute Shenzhen 518057 Guangdong China.

出版信息

Chem Sci. 2022 Mar 16;13(17):4762-4769. doi: 10.1039/d1sc06701j. eCollection 2022 May 4.

DOI:10.1039/d1sc06701j
PMID:35655875
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9067565/
Abstract

This study described palladium-catalyzed chemoselective direct α-arylation of carbonyl compounds with chloroaryl triflates in the Ar-Cl bond. The Pd/SelectPhos system showed excellent chemoselectivity toward the Ar-Cl bond in the presence of the Ar-OTf bond with a broad substrate scope and excellent product yields. The electronic and steric hindrance offered by the -PR group of the ligand with the C2-alkyl group was found to be the key factor affecting the reactivity and chemoselectivity of the α-arylation reaction. The chemodivergent approach was also successfully employed in the synthesis of flurbiprofen and its derivatives (, -OMe and -F).

摘要

本研究描述了钯催化羰基化合物与氯代芳基三氟甲磺酸酯在Ar-Cl键处进行的化学选择性直接α-芳基化反应。在Ar-OTf键存在的情况下，Pd/SelectPhos体系对Ar-Cl键表现出优异的化学选择性，底物范围广泛且产物收率优异。发现配体的-PR基团与C2-烷基提供的电子和空间位阻是影响α-芳基化反应活性和化学选择性的关键因素。化学发散法也成功应用于氟比洛芬及其衍生物（-OMe和-F）的合成。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5100/9067565/d85d86f9f6ac/d1sc06701j-s9.jpg
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