579-07-7Relevant articles and documents
Catalyst-Free and Transition-Metal-Free Approach to 1,2-Diketones via Aerobic Alkyne Oxidation
Shen, Duyi,Wang, Hongyan,Zheng, Yanan,Zhu, Xinjing,Gong, Peiwei,Wang, Bin,You, Jinmao,Zhao, Yulei,Chao, Mianran
, p. 5354 - 5361 (2021/05/05)
A catalyst-free and transition-metal-free method for the synthesis of 1,2-diketones from aerobic alkyne oxidation was reported. The oxidation of various internal alkynes, especially more challenging aryl-alkyl acetylenes, proceeded smoothly with inexpensive, easily handled, and commercially available potassium persulfate and an ambient air balloon, achieving the corresponding 1,2-diketones with up to 85% yields. Meanwhile, mechanistic studies indicated a radical process, and the two oxygen atoms in the 1,2-diketons were most likely from persulfate salts and molecular oxygen, respectively, rather than water.
Ozonolysis of Alkynes - A Flexible Route to Alpha-Diketones: Synthesis of AI-2
Alterman, Joshua L.,Halverson, Larry J.,Kraus, George A.,Stroud, Marissa Roghair,Vang, Dua X.
supporting information, p. 7424 - 7426 (2020/10/05)
A mild procedure for the low-temperature conversion of alkynes to diketones has been developed and employed in the synthesis of AI-2.
Direct Umpolung Morita–Baylis–Hillman like α-Functionalization of Enones via Enolonium Species
Arava, Shlomy,Kapanaiah, Raja,Pathe, Gulab K.,Santra, Sourav K.,Szpilman, Alex M.
supporting information, p. 15171 - 15175 (2020/07/04)
Herein we report on the umpolung of Morita–Baylis–Hillman type intermediates and application to the α-functionalization of enone C?H bonds. This reaction gives direct access to α-chloro-enones, 1,2-diketones and α-tosyloxy-enones. The latter are important intermediates for cross-coupling reaction and, to the best of our knowledge, cannot be made in a single step from enones in any other way. The proposed mechanism is supported by spectroscopic studies. The key initial step involves conjugate attack of an amine (DABCO or pyridine), likely assisted by hypervalent iodine acting as a Lewis acid leading to formation of an electrophilic β-ammonium-enolonium species. Nucleophilic attack by acetate, tosylate, or chloride anion is followed by base induced elimination of the ammonium species to give the noted products. Hydrolysis of α-acetoxy-enones lead to formation of 1,2-diketones. The α-tosyl-enones participate in Negishi coupling reactions under standard conditions.