NiH-Catalyzed Reductive Hydrocarbonation of Enol Esters and Ethers

Chiral dialkyl carbinols and their derivatives are significant synthetic building blocks in organic chemistry and related fields. The development of convenient and efficient methods to access these compounds has long been an important endeavor. Herein, we report a NiH-catalyzed reductive hydroalkylation and hydroarylation of enol esters and ethers. alpha-Oxoalkyl organonickel species were generated in situ in a catalytic mode and then participated in cross-coupling with alkyl or aryl halides. This approach enabled C(sp(3))-C(sp(3)) and C(sp(3))-C(sp(2)) bond formation under mild reductive conditions with simple operations, thereby boosting a broad substrate scope and good functional compatibility. Esters of enantioenriched dialkyl carbinols were accessed in a catalytic asymmetric version. Mechanistic studies demonstrated that this reaction proceeded through a syn-addition of Ni-H intermediate to an enol ester with high regio- and enantioselectivity. [GRAPHICS] .

Automated summary

In this study, a new method for the synthesis of chiral dialkyl carbinols was reported. The cross-coupling reaction between alkyl and aryl with enol esters and ethers was catalyzed by NiH, achieving the formation of C-C bonds with simple operations and a broad substrate scope.