Publication Date:
2011-04-23
Description:
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-lambda(3)-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.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Ochiai, Masahito -- Miyamoto, Kazunori -- Kaneaki, Takao -- Hayashi, Satoko -- Nakanishi, Waro -- New York, N.Y. -- Science. 2011 Apr 22;332(6028):448-51. doi: 10.1126/science.1201686.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Graduate School of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505, Japan. mochiai@ph.tokushima-u.ac.jp〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/21512029" target="_blank"〉PubMed〈/a〉
Keywords:
Adamantane/chemistry
;
Alkanes/*chemistry
;
Amination
;
Amines/*chemistry
;
Bromobenzenes/*chemistry
;
Carbon/chemistry
;
Hydrocarbons, Brominated/*chemistry
;
Hydrogen/chemistry
;
Kinetics
;
Physicochemical Processes
;
Stereoisomerism
;
Temperature
;
Thermodynamics
Print ISSN:
0036-8075
Electronic ISSN:
1095-9203
Topics:
Biology
,
Chemistry and Pharmacology
,
Computer Science
,
Medicine
,
Natural Sciences in General
,
Physics
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