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.
Original language | English (US) |
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Pages (from-to) | 13253-13260 |
Number of pages | 8 |
Journal | Journal of the American Chemical Society |
Volume | 141 |
Issue number | 33 |
DOIs | |
State | Published - Aug 21 2019 |
All Science Journal Classification (ASJC) codes
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry