Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations.

ABSTRACT: Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium-weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond-forming reactions, including carbon-hydrogen (C-H) insertion into unactivated sp³ C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered

SUBMITTER: Popov S 

PROVIDER: S-EPMC6688626 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature