Access to Enantioenriched 1,<i>n</i>-Diamines via Ni-Catalyzed Hydroamination of Unactivated Alkenes with Weakly Coordinating Groups
Pengfei Yang, Jian-Xing Liang, Han‐Tong Zhao, Wei Shu
Abstract
Enantioenriched 1,2- and 1,3-diamines with chiral α-branched aliphatic amine motifs are important substructures in bioactive compounds and related molecules and serve as privileged chiral ligands in both organo- and transition-metal-catalysis. However, direct access to such structural motifs remains a formidable challenge. Herein, a straightforward method to access 1,n-diamines (n = 2, 3, 4) containing a chiral α-branched aliphatic amine is achieved by Ni-catalyzed asymmetric hydroamination of unactivated aliphatic alkenes. Facilitated by a remote weakly coordinating group, the reaction is applicable to both terminal and internal unactivated alkenes, delivering enantioenriched 1,2-, 1,3-, and 1,4-diamine precursors in good yields and excellent enantioselectivities with diverse substitution patterns. Unactivated aliphatic alkenes serve as secondary alkyl nucleophile surrogates in the presence of Ni–H, forging the C–N bond enantioselectively with aminating reagents. In addition, the reaction proceeds at room temperature with excellent functional group tolerance.