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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 that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.


Popov, S.; Shao, B.; Bagdasarian, A. L.; Benton, T. R.; Zou, L.; Yang, Z.; Houk, K. N.; Nelson, H. M., Science 2018, 361, 381Contributed by Steven BacharachReposted from Computational Organic Chemistry with permissionA recent paper by Papov, Shao, Bagdasarian,...
A recent paper by Papov, Shao, Bagdasarian, Benton, Zou, Yang, Houk, and Nelson uncovers a vinyl cation insertion reaction that once again involves dynamic effects.1They find that vinyl triflates and cyclic vinyl triflates will react with [Ph3C]+[HCB11Cl11]–...