4019-61-8Relevant academic research and scientific papers
Characterization of Solvent and Deuterium Isotope Effects on Nonadiabatic Proton Transfer in the Benzophenone/N,N-Dimethylaniline Contact Radical Ion Pair
Peters, Kevin S.,Kim, Ganghyeok
, p. 2598 - 2606 (2004)
The dynamics of proton transfer within a variety of substituted benzophenones/N,N-dimethylaniline contact radical ion pairs are examined in a wide range of solvent polarities. The correlation of the rate constants with the thermodynamic driving force reveals both a normal and inverted region for proton transfer in solvents with an ET30 value of less than 43.1; in solvents with ET30 greater than 43.8, only the normal region is observed. Also, the kinetic deuterium isotope effect is examined. The solvent and isotope dependence for the transfer process is examined within the context of the Lee - Hynes model for nonadiabatic proton transfer. The theoretical analysis of the experimental data suggests that the reaction path for proton transfer involves tunneling. Conventional transition state theory with the inclusion of tunneling in the region of the transition state cannot account for the observed kinetic behavior.
Cercosporin-photocatalyzed sp3 (C-H) activation for the synthesis of pyrrolo[3,4-: C] quinolones
Li, Jia,Bao, Wenhao,Zhang, Yan,Rao, Yijian
, p. 8958 - 8962 (2019)
We reported a new method that visible light along with cercosporin, one of the naturally occurring perylenequinonoid pigments with excellent properties of photosensitization, photocatalyzed sp3 (C-H) activation for the synthesis of pyrrolo[3,4-
Cr-Catalyzed Direct ortho-Aminomethylation of Phenols
Shi, Junbin,Wang, Yubin,Bu, Qingqing,Liu, Binyuan,Dai, Bin,Liu, Ning
, p. 17567 - 17580 (2021/12/17)
We developed a Cr-catalyzed strategy for the regioselective formation of Csp2–Csp3 bonds through the direct and efficient ortho-aminomethylation of N,N-dimethylanilines with phenols. The approach showed excellent site selectivity at the ortho-position of phenols and accommodated broad substrate scope and functional group compatibility for both N,N-dimethylanilines and phenols. Mechanistic studies revealed that the direct ortho-aminomethylation between N,N-dimethylanilines and phenols occurred via an ionic mechanism.
Cu-Catalyzed Cross-Dehydrogenative ortho-Aminomethylation of Phenols
Yu, Congjun,Patureau, Frederic W.
supporting information, p. 11807 - 11811 (2018/09/10)
A highly selective CuII-catalyzed cross-dehydrogenative ortho-aminomethylation of phenols with aniline derivatives is described. The corresponding C(sp2)?C(sp3) coupling products were obtained in moderate to excellent yields under mild reaction conditions and with a broad substrate scope. A radical mechanism is proposed.
Oxidative Cyclization Synthesis of Tetrahydroquinolines and Reductive Hydrogenation of Maleimides under Redox-Neutral Conditions
Yang, Xiu-Long,Guo, Jia-Dong,Lei, Tao,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
supporting information, p. 2916 - 2920 (2018/05/29)
A redox-neutral reaction without using any external oxidant and reductant in one pot is described. By combining a Ru(bpy)32+ photocatalyst and cobaloxime catalyst, a number of tertiary anilines can be oxidized by Ru(bpy)3
Metal-Free Geminal Difunctionalization of Diazocarbonyl Compounds: A One-Pot Multicomponent Strategy for the Construction of α,β-Diamino Carbonyl Derivatives
Zhu, Dan,Yao, Yuan,Zhao, Rong,Liu, Yang,Shi, Lei
supporting information, p. 4805 - 4809 (2018/03/21)
An unprecedented three-component domino oxidative coupling of diazocompounds for the efficient synthesis of α-azido-β-amino esters with non-activated dimethylamino compounds and simple TMSN3 was achieved. The main features of this method include metal-free catalysis, satisfactory functional group tolerance, general applicability in complex molecule architectures, and excellent diastereoselectivity in the presence of chiral auxiliaries. In addition, several related control experiments have been conducted to investigate the reaction mechanism.
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.
An efficient synthesis of [D6]leucocrystal violet
Yang, Weicheng,Luo, Yong,Liu, Weixia,Deng, Xiaojun,Du, Xiaoning,Li, Meihua
experimental part, p. 211 - 213 (2012/05/20)
This report presents an efficient synthesis of [D6]leucocrystal violet. Esterification of p-toluenesulphonyl chloride with [D4]methanol provided [D 3]methyl p-toluenesulphonate, which was used to methylate aniline to give [D6]N, N-di
Iron/amino acid catalyzed direct N-alkylation of amines with alcohols
Zhao, Yingsheng,Foo, Siong Wan,Saito, Susumu
supporting information; experimental part, p. 3006 - 3009 (2011/05/04)
(Chemical Equation Presented) Ironing it out: The straightforward N-alkylation using alcohols and iron/amino acid catalysis is described (see scheme). The reaction does not proceed by the conventional "borrowing hydrogen" mechanism, but appears to involve a substitution pathway (S N) at the sp3 carbon atom bearing the hydroxy group of the alcohol. Developing a catalyst that is effective at a near neutral pH was key to the successful N-alkylation.
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
