Enantioselective Double Carbonylation Enabled by High-Valent Palladium Catalysis
Jian Han, Bo-Wen Xiao, Tian‐Yu Sun, Min Wang, Long Jin, Wangzhi Yu, Yuqin Wang, Dongmei Fang, Yan Zhou, Xiao‐Feng Wu, Yun‐Dong Wu, Jian Liao
Abstract
Palladium-catalyzed carbonylation reactions are efficient methods for synthesizing valuable molecules. However, realizing a carbonylation with excellent yield and chemo-, regio-, and enantioselectivities by classical low-valent palladium catalysis is highly challenging. Herein, we describe an enantioselective carbonylation reaction using a high-valent palladium catalysis strategy and employing a chiral sulfoxide phosphine (SOP) ligand. This double aminocarbonylation reaction begins with the formation of a carbamoylpalladium(II) species, which undergoes enantioselective oxidative addition with a cyclic diaryliodonium salt to generate a palladium(IV) intermediate, followed by a second CO insertion and reductive elimination. The mechanism has been illustrated with experimental and computational studies.