108062-64-2Relevant articles and documents
Photoinduced C—C Bond Cleavage and Oxidation of Cycloketoxime Esters
Zhao, Binlin,Tan, Hui,Chen, Cheng,Jiao, Ning,Shi, Zhuangzhi
, p. 995 - 999 (2018)
A novel structural reorganization of cycloketoxime esters beyond the traditional Beckmann rearrangement process has been established to build cyano-containing ketones in the presence of photocatalyst. This novel transformation is remarkable with selective C—C bond cleavage and an oxidation process enabled by DMSO used as the solvent, oxidant, and oxygen source avoiding acid, base and toxic cyanide salts as the cyano source. Further applications in late-stage modification of complex and chiral molecules have also been reported.
General and efficient insertions of carbons carrying aryl and heteroaryl groups: Synthesis of α-Aryl- And α-heteroaryl-substituted ketones
Katritzky, Alan R.,Toader, Dorin,Xie, Linghong
, p. 7571 - 7577 (2007/10/03)
Anions formed from the lithiation of a variety of 1-(arylmethyl)- and 1-(heteroarylmethyl)-benzotriazoles 1 with n-BuLi underwent addition to aliphatic and aromatic aldehydes and cyclic and acyclic ketones. Subsequent in situ thermal rearrangements of the intermediates in the presence of zinc bromide provided one-carbon chain-extended or ring-expanded α-aryl- and α-heteroaryl-substituted ketones 2 in moderate to excellent yields in simple one-pot operations with excellent regioselectivity in most cases. Substituent effects on the relative migration rates were investigated in the insertion reactions of 1-(4-methoxybenzyl)benzotriazole (1e) with XC6H4-COPh. The small and negative Hammett ρ+ value (-0.92) suggested that the rearrangements proceed via early, reagent-like, electron deficient transition states.
