C–H Alkylation via Multisite-Proton-Coupled Electron Transfer of an Aliphatic C–H Bond
(2019) Journal of the American chemical society — Vol. 141, n° 33, p. 13253-13260 (2019)
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- Authors
Zhu, Qilei 
Alexanian, Erik J.
- Abstract
- The direct, site-selective alkylation of unactivated C(sp3)–H bonds in organic substrates is a long-standing goal in synthetic chemistry. General approaches to the activation of strong C–H bonds include radical-mediated processes involving highly reactive intermediates, such as heteroatom-centered radicals. Herein, we describe a catalytic, intermolecular C–H alkylation that circumvents such reactive species via a new elementary step for C–H cleavage involving multisite-proton-coupled electron transfer (multisite-PCET). Mechanistic studies indicate that the reaction is catalyzed by a noncovalent complex formed between an iridium(III) photocatalyst and a monobasic phosphate base. The C–H alkylation proceeds efficiently using diverse hydrocarbons and complex molecules as the limiting reagent and represents a new approach to the catalytic functionalization of unactivated C(sp3)–H bonds.
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Citations
Morton, C. M., Zhu, Q., Ripberger, H., Troian-Gautier, L., Toa, Z. S. D., Knowles, R. R., & Alexanian, E. J. (2019). C–H Alkylation via Multisite-Proton-Coupled Electron Transfer of an Aliphatic C–H Bond. Journal of the American chemical society, 141(33), 13253-13260. https://doi.org/10.1021/jacs.9b06834 (Original work published 2019)