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

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 intramo...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2018-07, Vol.361 (6400), p.381-387
Main Authors: Popov, Stasik, Shao, Brian, Bagdasarian, Alex L, Benton, Tyler R, Zou, Luyi, Yang, Zhongyue, Houk, K N, Nelson, Hosea M
Format: Article
Language:English
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Summary: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 sp 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.
ISSN:0036-8075
1095-9203
1095-9203
DOI:10.1126/science.aat5440