7506-97-0Relevant academic research and scientific papers
One-Pot Synthesis of Tertiary Amides from Organic Trichlorides through Oxygen Atom Incorporation from Air by Convergent Paired Electrolysis
Luo, Zhongli,Imamura, Kenji,Shiota, Yoshihito,Yoshizawa, Kazunari,Hisaeda, Yoshio,Shimakoshi, Hisashi
, p. 5983 - 5990 (2021/05/04)
A convergent paired electrolysis catalyzed by a B12 complex for the one-pot synthesis of a tertiary amide from organic trichlorides (R-CCl3) has been developed. Various readily available organic trichlorides, such as benzotrichloride and its derivatives, chloroform, dichlorodiphenyltrichloroethane (DDT), trichloro-2,2,2-trifluoroethane (CFC-113a), and trichloroacetonitrile (CNCCl3), were converted to amides in the presence of tertiary amines through oxygen incorporation from air at room temperature. The amide formation mechanism in the paired electrolysis, which was mediated by a cobalt complex, was proposed.
Visible light-driven photocatalytic duet reaction catalyzed by the B12-rhodium-titanium oxide hybrid catalyst
Shichijo, Keita,Fujitsuka, Mamoru,Hisaeda, Yoshio,Shimakoshi, Hisashi
supporting information, (2019/12/24)
The hybrid catalyst composed of the B12 complex and rhodium ion (Rh3+) modified titanium oxide was synthesized for the visible light-driven B12 inspired catalytic reaction. The hybrid catalyst contains 4.93 × 10?6 molg?1 of the B12 complex and 5.43 × 10?5 molg?1 of the Rh(III) ion on the surface of titanium oxide. Visible light irradiation (λ ≧ 420 nm) of the hybrid catalyst in the presence of triethylamine (Et3N) as a sacrificial reagent showed absorption at 390 nm, typical for the Co(I) state of the B12 complex monitored by diffuse reflectance UV–vis analysis, which imply that electron transfer from the titanium oxide to Co(III) center of the B12 complex occurred by the visible light irradiation. Benzotrichloride was converted to N,N-diethylbenzamide by the visible light irradiation catalyzed by the hybrid catalyst in air at room temperature. Both the conduction band electron and valence band hole of the catalyst were utilized for the reaction to form the amide product. The reaction mechanism of the duet reaction was proposed.
Visible Light-Driven, One-pot Amide Synthesis Catalyzed by the B12 Model Complex under Aerobic Conditions
Tian, Hui,Shimakoshi, Hisashi,Ono, Toshikazu,Hisaeda, Yoshio
, p. 237 - 240 (2018/12/13)
A visible light responsive catalytic system with the B12 complex as the catalyst and [Ir(dtbbpy)(ppy)2]PF6 as the photosensitizer was developed. It provides a convenient and efficient way to synthesize amides. Based on this method, trichlorinated organic compounds were converted into amides in the presence of an amine under aerobic conditions at room temperature in a one-pot procedure. Various trichlorinated organic compounds and an amine source, such as primary, secondary, and cyclic amines, have been evaluated for this transformation, providing the expected products in moderate to excellent yields. Notably, product formation depended on the reaction atmosphere where the amide was obtained under aerobic conditions while partially dechlorinated products were obtained under anaerobic conditions. As this protocol is free from hazardous reagents, extra additives, noble metals, and dangerous gas, the present method provides a novel and efficient approach for amide synthesis under mild and easily controlled conditions.
