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Highly Regioselective Amination of Unactivated Alkanes by Hypervalent Sulfonylimino-λ3-Bromane

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Science  22 Apr 2011:
Vol. 332, Issue 6028, pp. 448-451
DOI: 10.1126/science.1201686

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Abstract

Amination of alkanes has generally required metal catalysts and/or high temperatures. Here we report that simple exposure of a broad range of alkanes to N-triflylimino-λ3-bromane 1 at ambient temperature results in C–H insertion of the nitrogen functionality to afford triflyl-substituted amines in moderate to high yields. Marked selectivity for tertiary over secondary C–H bonds was observed; primary (methyl) C–H bonds were inert. Addition of hexafluoroisopropanol to inhibit decomposition of 1 dramatically improved the C–H amination efficiencies. Second-order kinetics, activation parameters (negative activation entropy), deuterium isotope effects, and theoretical calculations suggest a concerted asynchronous bimolecular transition state for the metal-free C–H amination event.

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