1452220-11-9Relevant academic research and scientific papers
Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils
Zhu, Jia-Liang,Tsai, Yi-Ting
, p. 813 - 828 (2020/12/22)
The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.
Visible light-induced aerobic oxidation of diarylalkynes to α-diketones catalyzed by copper-superoxo at room temperature
Charpe, Vaibhav Pramod,Hwang, Kuo Chu,Sagadevan, Arunachalam
supporting information, p. 4426 - 4432 (2020/08/10)
We have developed the visible light induced simple copper(ii) chloride catalyzed oxidation of diarylacetylenes to α-diketones by molecular oxygen at room temperature. The in situ generated copper(ii)-superoxo complex is a light-absorbing species that oxidizes inert diarylacetylenes to α-diketones. In contrast to reported photochemical processes, the current oxidation protocol does not require any exogenous photocatalyst or radical initiator. The green chemistry metrics evaluation signifies that the E-factor for the current oxidation process is ～2.3 times better than that of reported photochemical processes. The current reaction scores 63 on the EcoScale of 0-100, indicating an adequate synthesis process. Thus, the overall oxidation process is simple, environmentally benign, and economically feasible. This journal is
Synthesis of 1,2-Diketones via a Metal-Free, Visible-Light-Induced Aerobic Photooxidation of Alkynes
Liu, Xu,Cong, Tiantian,Liu, Ping,Sun, Peipei
, p. 7256 - 7261 (2016/08/30)
1,2-Diketones were synthesized by the oxidation of corresponding alkynes using air as the oxidant under metal-free conditions upon irradiation of blue light. A cheap and readily available organic dye, eosin Y, was used as the photocatalyst. For various substituents on the aryl ring, the reaction proceeded smoothly to give the dicarbonylation products in moderate to good yields. Some oxidation-sensitive groups, such as formyl and the carbon-carbon double bond, were tolerated under the developed reaction conditions.
