Bridging Theory and Experiment in Establishing Mechanisms of Chemical Reactions

来源 :第五届岭南有机化学论坛暨华南理工大学-兰州大学有机化学双边论坛 | 被引量 : 0次 | 上传用户:xxlxxl123
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In this lecture,mechanistic studies of several catalytic reactions will be discussed.1(1) The study of hydrosilylation of alkynes catalyzed by Trosts Cp*Ru(NCMe)3PF6-catalyst led to the proposal of a novel reaction mechanism:oxidative-added proton addition to alkyne to form a metallocyclopropene intermediate,followed by silyl migration to give unusual Markovnikov regiochemistry and trans-addition stereochemistry.2 This mechanism can be extended to a series of reactions.3-4(2) Unexpected meta product in copper-catalyzed arylation of anilide can be explained by a Heck-like four-membered ring transition state involving a Cu(Ⅲ)-Ph species.This Cu(Ⅰ)/Cu(Ⅲ) mechanism is supported by a series of experiments.5(3) Mechanistic understanding has been developed for direct distal meta-C-H bond(more than ten bonds away) activation in tethered arene containing a remote nitrile.6-7 The mechanism can be extended to understand amino acid promoted enantioselective C-H bond activation.
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Trifluoromethylated compounds are of particular interest in the field of pharmaceuticals,and agrochemicals due to the unique characteristics of the trifluoromet
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