Ni-catalyzed hydroalkylation of olefins with N-sulfonyl amines.

ABSTRACT: Hydroalkylation, the direct addition of a C(sp³)-H bond across an olefin, is a desirable strategy to produce valuable, complex structural motifs in functional materials, pharmaceuticals, and natural products. Herein, we report a reliable method for accessing α-branched amines via nickel-catalyzed hydroalkylation reactions. Specifically, by using bis(cyclooctadiene)nickel (Ni(cod)₂) together with a phosphine ligand, we achieved a formal C(sp³)-H bond insertion reaction between olefins and N-sulfonyl amines without the need for an external hydride source. The amine not only provides the alkyl motif but also delivers hydride to the olefin by means of a nickel-engaged β-hydride elimination/reductive elimination process. This method provides a platform for constructing chiral α-branched amines by using a P-chiral ligand, demonstrating its potential utility in organic synthesis. Notably, a sulfonamidyl boronate complex formed in situ under basic conditions promotes ring-opening of the azanickellacycle reaction intermediate, leading to a significant improvement of the catalytic efficiency.

SUBMITTER: Yan XB 

PROVIDER: S-EPMC8497516 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature