Palladium-Catalyzed Carbonylation of C-H Bonds for the Synthesis of Carbonyl Compounds
作者单位：Department of Chemistry & Materials Science Northwest University
会议名称：《中国化学会第十四届全国有机合成化学学术研讨会》
会议日期：2017年
学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学]
基 金：国家自然科学基金(No.21622203 21472147)资助项目
关 键 词：palladium-catalyzed carbonylation enamines C-H activation
摘 要：Carbonylation reactions have proven to be powerful tools for construction of carbonyl compounds. However, transition metal catalyzed carbonylation of C-H bonds with CO remains challenging. In recent years, we have developed palladium-catalyzed carbonylation reactions of various anilines and enamides. Especially, palladium-catalyzed C-H/N-H double carbonylation of secondary alkyl anilines was developed for straightforward synthesis of isatoic anhydrides, and carbonylation of alkenyl C-H bonds of enamides was developed for the synthesis of 1,3-oxazin-6-ones. Furthermore, palladium-catalyzed carbonylative Suzuki-Miyaura coupling of indole and phenyl boronic acid in the presence of I was developed for the synthesis of indol-3-yl aryl ketones. Very recently, palladium-catalyzed regioselective oxidative carbonylation of tri-substituted alkenes with CO and alcohols for the synthesis of α,β-unsaturated esters has been developed. The experiment results and DFT calculations suggested that the oxidative carbonylation proceeded through alkoxylation of palladium catalyst, CO and alkenyl C=C double bond migratory insertion, β-(N)H elimination and tautomerization cascade steps.