Ferric chloride-catalyzed decarboxylative alkylation of β-keto acids with benzylic alcohols  

作　　者：YANG CuiFeng SHEN Chen LI HaiHua TIAN ShiKai 

机构地区：[1]Joint Laboratory of Green Synthetic Chemistry,Department of Chemistry,University of Science and Technology of China,Hefei 230026,China [2]Key Laboratory of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Chinese Science Bulletin》2012年第19期2377-2381,共5页

基　　金：supported by the National Natural Science Foundation of China (21172206,20972147,and J1030412);the National Basic Research Program of China (2010CB833300);the Program for Changjiang Scholars and Innovative Research Team in University (IRT1189)

摘　　要：β-Keto acids are unstable to heat,acids,and bases,and have rarely been employed as carbon nucleophiles for the formation of carbon-carbon bonds.In this context,an efficient decarboxylative alkylation reaction of β-keto acids with benzylic alcohols has been developed,for the first time,through sequential cleavage of carbon-oxygen and carbon-carbon bonds.In the presence of 10 mol% of ferric chloride,a range of β-keto acids smoothly undergo decarboxylative alkylation with benzylic alcohols to give structurally diverse unsymmetric ketones in moderate to excellent yields and with extremely high regioselectivity.Preliminary mechanistic studies indicate that the reaction proceeds through an SN1 alkylation followed by decarboxylation.β-Keto acids are unstable to heat, acids, and bases, and have rarely been employed as carbon nucleophiles for the formation of carbon-carbon bonds. In this context, an efficient decarboxylative alkylation reaction of β-keto acids with benzylic alcohols has been developed, for the first time, through sequential cleavage of carbon-oxygen and carbon-carbon bonds. In the presence of 10 mol% of ferric chloride, a range of β-keto acids smoothly undergo decarboxylative alkylation with benzylic alcohols to give structurally diverse unsymmetric ketones in moderate to excellent yields and with extremely high regioselectivity. Preliminary mechanistic studies indicate that the reaction proceeds through an SN1 alkylation followed by decarboxylation.

关 键 词：烷基化反应 三氯化铁 酮酸 脱羧 苄醇 催化 区域选择性 连续裂解 

分 类 号：O643.32[理学—物理化学]