DFT insight into asymmetric alkyl-alkyl bond formation via nickel-catalysed enantioconvergent reductive coupling of racemic electrophiles with olefins.

ABSTRACT: A DFT study has been conducted to understand the asymmetric alkyl-alkyl bond formation through nickel-catalysed reductive coupling of racemic alkyl bromide with olefin in the presence of hydrosilane and K₃PO₄. The key findings of the study include: (i) under the reductive experimental conditions, the Ni(ii) precursor is easily activated/reduced to Ni(0) species which can serve as an active species to start a Ni(0)/Ni(ii) catalytic cycle. (ii) Alternatively, the reaction may proceed via a Ni(i)/Ni(ii)/Ni(iii) catalytic cycle starting with a Ni(i) species such as Ni(i)-Br. The generation of a Ni(i) active species via comproportionation of Ni(ii) and Ni(0) species is highly unlikely, because the necessary Ni(0) species is strongly stabilized by olefin. Alte

SUBMITTER: Zhang CS 

PROVIDER: S-EPMC8966719 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature