51954-17-7Relevant articles and documents
Palladium-catalyzed allylic alkylation dearomatization of β-naphthols and indoles withgem-difluorinated cyclopropanes
Fu, Zhiyuan,Zhu, Jianping,Guo, Songjin,Lin, Aijun
, p. 1262 - 1265 (2021)
A palladium-catalyzed allylic alkylation dearomatization of β-naphthols and indoles withgem-difluorinated cyclopropanes has been developed. This reaction provided an efficient route to access 2-fluoroallylic β-naphthalenones and indolenines bearing quaternary carbon centers in good yields with highZ-selectivityviaC-C bond activation, C-F bond cleavage and the dearomatization process, benefiting from the wide substrate scope and good functional group tolerance. Moreover, 2-fluoroallylic furanoindoline and pyrroloindolines were achieved in good efficiencyviacascade allylic alkylation, dearomatization and cyclization processes in the presence of Et3B.
Reaction of (bromodifluoromethyl)trimethylsilane with HMPA: Structural studies
Dilman, Alexander D.,Hu, Jinbo,Korlyukov, Alexander A.,Supranovich, Vyacheslav I.,Volodin, Alexander D.
, (2021)
The crystal structure of a low melting difluorinated silicon reagent (bromodifluoromethyl)trimethylsilane is described. Hexamethylphosphoramide (HMPA) serves as an efficient Lewis basic activator to decompose the silicon reagent to generate difluorocarbene along with the formation of silyl-capped HMPA cation. The bromide salt with Me3Si-HMPAcation was also obtained by interaction of bromotrimethylsilane with HMPA and was characterized by X-ray analysis. Interaction of silanes with HMPA was evaluated by quantum chemical calculations, which demonstrated that the Lewis base provides a significant decrease of the transition state energy for the generation of difluorocarbene by an attack at the silicon atom.
Difluoromethylation of alcohols with TMSCF2Br in water: A new insight into the generation and reactions of difluorocarbene in a two-phase system
Zhang, Rongyi,Ni, Chuanfa,Xie, Qiqiang,Hu, Jinbo
supporting information, (2020/11/10)
Although many difluorocarbene-involved reactions can be performed in the presence of water, the reaction of difluorocarbene using water as the only reaction medium is rare. By using TMSCF2Br as a unique difluorocarbene reagent and KHF2 as a mild activator, the difluoromethylation of liquid alcohols in water is described. This research not only develops an environmentally benign process for the synthesis of difluoromethyl ethers, but also provides a new insight into the generation and reactions of difluorocarbene in an oil-water two-phase system.