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Article Dans Une Revue Journal of the American Chemical Society Année : 2021

Catalytic Intermolecular C(sp3)–H Amination: Selective Functionalization of Tertiary C–H Bonds vs Activated Benzylic C–H Bonds

Résumé

A catalytic intermolecular amination of non-activated tertiary C(sp 3)−H bonds (BDE of 96 kcal.mol-1) is reported for substrates displaying an activated benzylic site (BDE of 85 kcal.mol-1). The tertiary C(sp 3)−H bond is selectively functionalized to afford a,a,a-trisubstituted amides in high yields. This unusual site-selectivity results from the synergistic combination of Rh2(Stfpttl)4, a rhodium(II) complex with a well-defined catalytic pocket, with tert-butylphenol sulfamate (TBPhsNH2), which leads to a discriminating rhodium-bound nitrene species under mild oxidative conditions. This catalytic system is very robust and the reaction was performed on a 50 mmoles-scale with only 0.01 mol% of catalyst. The TBPhs group can be removed under mild conditions to afford the corresponding NH-free amines.
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Dates et versions

hal-03344926 , version 1 (15-09-2021)

Identifiants

Citer

Erwan Brunard, Vincent Boquet, Elsa van Elslande, Tanguy Saget, Philippe Dauban. Catalytic Intermolecular C(sp3)–H Amination: Selective Functionalization of Tertiary C–H Bonds vs Activated Benzylic C–H Bonds. Journal of the American Chemical Society, 2021, 143 (17), pp.6407-6412. ⟨10.1021/jacs.1c03872⟩. ⟨hal-03344926⟩
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