Access to Enantioenriched 1,n-Diamines via Ni-Catalyzed Hydroamination of Unactivated Alkenes with Weakly Coordinating Groups

Enantioenriched 1,2- and 1,3-diamines with chiral alpha-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 alpha-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.

Automated summary

In this study, a straightforward method to access enantioenriched 1,n-diamines containing a chiral alpha-branched aliphatic amine is achieved through Ni-catalyzed asymmetric hydroamination. This method delivers good yields and excellent enantioselectivities with diverse substitution patterns, and exhibits excellent functional group tolerance.