Alkyl halides as both hydride and alkyl sources in catalytic regioselective reductive olefin hydroalkylation.

ABSTRACT: Among the plethora of catalytic methods developed for hydrocarbofunctionalization of olefins to date, reactions that regioselectively install a functionalized alkyl unit at the 2-position of a terminal unactivated C=C bond to afford branched products are scarce. Here, we show that a Ni-based catalyst in conjunction with a stoichiometric reducing agent promote Markovnikov-selective hydroalkylation of unactivated alkenes tethered to a recyclable 8-aminoquinaldine directing auxiliary. These mild reductive processes employ readily available primary and secondary haloalkanes as both the hydride and alkyl donor. Reactions of alkenyl amides with ? five-carbon chain length regioselectively afforded ?-alkylated products through remote hydroalkylation, underscoring the fidelity of the catalytic process and the directing group's capability in stabilizing five-membered nickelacycle intermediates. The operationally simple protocol exhibits exceptional functional group tolerance and is amenable to the synthesis of bioactive molecules as well as regioconvergent transformations.

SUBMITTER: Chen X 

PROVIDER: S-EPMC7673021 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature