1309687-95-3Relevant academic research and scientific papers
Highly regioselective amination of unactivated alkanes by hypervalent sulfonylimino-δ3-bromane
Ochiai, Masahito,Miyamoto, Kazunori,Kaneaki, Takao,Hayashi, Satoko,Nakanishi, Waro
scheme or table, p. 448 - 451 (2011/10/31)
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-δ3-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.
