Palladium-Catalyzed Regio- and Enantioselective Synthesis of Allylic Amines Featuring Tetrasubstituted Tertiary Carbons

The first asymmetric synthesis of α,α-disubstituted allylic N-arylamines based on a palladium-catalyzed allylic amination has been developed. The protocol uses highly modular vinyl cyclic carbonates and unactivated aromatic amine nucleophiles as substrates. The catalytic process features minimal waste production, ample scope in reaction partners, high asymmetric induction up to 97% ee, and operational simplicity.本研究开发了首例基于钯催化烯丙基胺化反应的α,α-二取代烯丙基N-芳基胺不对称合成方法。该合成方案以模块化程度极高的乙烯基环碳酸酯与未活化芳香胺亲核试剂作为反应底物。该催化体系具有废弃物生成量极低、反应底物适配范围广泛、不对称诱导效果优异，最高对映体过量（enantiomeric excess, ee）值可达97%，且操作简便的优势。