Mechanistic investigation of oxidative Mannich reaction with tert-butyl hydroperoxide. the role of transition metal salt

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[1] Ratnikov, Maxim O.
[2] Doyle, Michael P.
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Doyle, M.P. (mdoyle3@umd.edu) | 1600年 / American Chemical Society卷 / 135期
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A general mechanism is proposed for transition metal-catalyzed oxidative Mannich reactions of N; N-dialkylanilines with tert-butyl hydroperoxide (TBHP) as the oxidant. The mechanism consists of a rate-determining single electron transfer (SET) that is uniform from 4-methoxy- to 4-cyano-N; N-dimethylanilines. The tert-butylperoxy radical is the major oxidant in the rate-determining SET step that is followed by competing backward SET and irreversible heterolytic cleavage of the carbon-hydrogen bond at the α-position to nitrogen. A second SET completes the conversion of N; N-dimethylaniline to an iminium ion that is subsequently trapped by the nucleophilic solvent or the oxidant prior to formation of the Mannich adduct. The general role of Rh2(cap) 4; RuCl2(PPh3)3; CuBr; FeCl; 3; and Co(OAc)2 in N; N-dialkylaniline oxidations by T-HYDRO is to initiate the conversion of TBHP to tert-butylperoxy radicals. A second pathway; involving O2 as the oxidant; exists for copper; iron; and cobalt salts. Results from linear free-energy relationship (LFER) analyses; kinetic and product isotope effects (KIE and PIE); and radical trap experiments of N; N-dimethylaniline oxidation by T-HYDRO in the presence of transition metal catalysts are discussed. Kinetic studies of the oxidative Mannich reaction in methanol and toluene are also reported. © 2013 American Chemical Society;
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