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Abstract A general and operationally convenient method for intermolecular amination of C(sp3)−H bonds is described. This technology allows for efficient functionalization of complex molecules, including numerous pharmaceutical targets. The combination of pivalonitrile as a solvent, Al2O3as an additive, and phenyl sulfamate as a nitrogen source affords differential reaction performance and substrate scope. Mechanistic data strongly implicate a pathway for catalyst decomposition that initiates with solvent oxidation, thus providing rationale for the marked influence of pivalonitrile on this reaction process.
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Rh(II)‐catalyzed Intermolecular Benzylic C(sp 3 )−H Alkylation of Methyl‐substituted Arenes by N ‐Aryl‐α‐diazo‐β‐amidoesters
Abstract Herein, a general approach to intermolecular benzylic C(sp3)−H alkylation of methyl‐substituted arenes is reported using metal carbenes derived fromN‐aryl‐α‐diazo‐β‐amidoesters and dirhodium catalysts. Alkylated products were formed in up to 81 % yield with demonstrated functional group tolerance, outpacing previous literature. The unique amide‐ester scaffolding can be exploited through various derivatizations for broad synthetic utility and provides a starting point for the development of selectivity rules and reactivity profiles for these intermolecular C(sp3)−H functionalizations.
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- Award ID(s):
- 2102472
- PAR ID:
- 10445230
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemCatChem
- Volume:
- 14
- Issue:
- 11
- ISSN:
- 1867-3880
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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