Teaching an old carbocation new tricks: Intermolecular C–H insertion reactions of vinyl cations
Year: 2018
Type: article
Abstract: Silicon smooths the way to vinyl cations Saturated carbon centers often undergo substitution reactions by initial cleavage of a carbon-halogen or carbon-oxygen bond, which leaves the carbon positively charged. Analogous cations have proven much harder to access from vinylic carbons that are engaged in double bonds. Popov et al. now show that silicon cations paired with noncoordinating anions can pull triflate groups off such vinylic carbons under ambient conditions (see the Perspective by Kennedy and Klumpp). The resultant vinyl cations react with simple alkanes through C–H insertion. Theoretical and mechanistic studies suggest that these reactions proceed through nonclassical pathways that bifurcate after the transition state. Science , this issue p. 381 ; see also p. 331
Source: Science
Institutions: University of California, Los Angeles, Jilin University
Language: English
Subfield: Spectroscopy
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, David and Lucile Packard Foundation, Alfred P. Sloan Foundation, National Natural Science Foundation of China, University of California, Irvine, National Institute of General Medical Sciences, Division of Chemistry, National Center for Complementary and Integrative Health
Awards: G1455760090, G2202643355, G3890010759, Experimental and Theoretical Investigations of Organic Reaction Rates and Mechanisms, G7040847368, Kinetically-Persistent Carbocationsin C-H Insertion Reactions and Biomimetic Cyclization Cascades, G7482864200, Development and validation of a high-throughput MicroED-driven platform technology for natural product discovery
OpenAlex ID: W2883358227