52866-87-2Relevant academic research and scientific papers
Mechanistic investigation of oxidative Mannich reaction with tert-butyl hydroperoxide. the role of transition metal salt
Ratnikov, Maxim O.,Doyle, Michael P.
supporting information, p. 1549 - 1557 (2013/03/14)
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.
Iron-catalyzed oxidative amidation of tertiary amines with aldehydes
Li, Yuanming,Jia, Fan,Li, Zhiping
supporting information, p. 82 - 86 (2013/03/13)
Unconventional couple: A new oxidative coupling protocol for amide bond formation has been developed (see scheme). The method provides an efficient and practical route for the synthesis of tertiary amides from readily available tertiary amines and aldehydes in the presence of a simple FeCl2 catalyst. Mechanistic studies indicated that a peroxide and an iminium ion act as the reactive intermediates in this oxidative amidation.
Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 CH bond and lewis acid catalysis
Wang, Ming-Zhong,Zhou, Cong-Ying,Wong, Man-Kin,Che, Chi-Ming
supporting information; experimental part, p. 5723 - 5735 (2010/08/20)
Ruthenium porphyrins (particularly [Ru(2,6-Cl2tpp)CO]; tpp = tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82
Highly efficient Cu-catalyzed oxidative coupling of tertiary amines and?siloxyfurans
Shen, Youming,Tan, Ze,Chen, De,Feng, Xunbo,Li, Mo,Guo, Can-Cheng,Zhu, Chengliang
body text, p. 158 - 163 (2009/04/06)
A mild, selective, and efficient protocol for the synthesis of γ-aminoalkyl butenolides via the oxidative coupling between tertiary amines and siloxyfurans catalyzed by simple copper salts was developed. Compared with the reported method, our method emplo
Oxidation of amines with hyper valent Tert-butylperoxyiodanes: Synthesis of imines and Tert-butylperoxyamino acetalsh
Ochiai, Masahito,Kajishima, Daisuke,Sueda, Takuya
, p. 71 - 76 (2007/10/03)
Reaction of secondary amines with 1-tert-butylperoxy-1,2-benziodoxol-3(1H)-one (2) undergoes dehydrogenation to afford imines in the presence of K2CO3, while oxidation of tertiary amines without base produces tert-butylperoxyamino acetals.
