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.

Catalytic addition of a carbon chain and a hydrogen across a double bond has often required an added hydride source. Here the authors show a method to add alkanes with an amino functionality to olefins, wherein a nickel catalyst uses the amine itself as the hydride source, obviating an external hydride reagent.