13657-45-9Relevant articles and documents
One-Pot Synthesis of α-Halo β-Amino Acid Derivatives via the Difunctional Coupling of Ethyl α-Diazoacetate with Silyl Halides and N, O -Acetals or Aromatic Tertiary Amines
Ogiwara, Yohei,Sakai, Norio,Sasaki, Kazuki,Suzuki, Hiroki
supporting information, p. 1823 - 1832 (2020/06/08)
The difunctionalization of ethyl α-diazoacetate (EDA) using silyl halides as a nucleophile and N, O -acetals as an electrophile under metal-free conditions is described. This process undergoes a novel three-component coupling (3-CC) reaction using EDA, which leads to a one-pot preparation of α-halo β-amino acid esters. Also, this protocol could be adapted to accept an electrophile composed of aromatic tertiary amines. In both 3-CC reactions, the key reaction intermediate is an iminium intermediate that can be easily and effectively generated either from N, O -acetals or from aromatic tertiary amines.
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.
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
