1042682-66-5Relevant articles and documents
Divergent Regio- and Stereoselective Gold-catalyzed Synthesis of α-Fluorosulfones and β-Fluorovinylsulfones from Alkynylsulfones
Zeng, Xiaojun,Liu, Shiwen,Hammond, Gerald B.,Xu, Bo
, p. 11977 - 11981 (2017)
We developed a widely applicable, highly efficient synthesis of α-fluorosulfone and β-fluorovinylsulfone catalyzed by gold. Starting with alkynyl sulfone 1, an [Au]/HF/N-oxide system gives α-fluorosulfone 3 via a gold carbene intermediate, and, if no N-oxide is used, direct addition of HF to 1 gives vinyl sulfone 4 via a vinylfluoro gold intermediate. Both methods have good functional group tolerance and the reactions can be conducted in ambient atmosphere.
Nucleophilic fluoroalkylation of α,β-enones, arynes, and activated alkynes with fluorinated sulfones: Probing the hard/soft nature of fluorinated carbanions
Ni, Chuanfa,Zhang, Laijun,Hu, Jinbo
, p. 5699 - 5713 (2008/12/21)
(Chemical Equation Presented) We have successfully accomplished the nucleophilic fluoroalkylation of α,β-enones, arynes, and activated alkynes with fluorinated sulfones. It was found that for acylic α,β-enones, although the reaction medium and the structure of the enones can all influence the regioselectivity of the nucleophilic alkylation reactions, the hard/soft nature of the carbanions played a major role. By using the 1,4- and 1,2-addition product ratio as a probe to determine the hard/soft nature of the above-mentioned four halogenated carbanions, the order of the softness of these carbanions can be given as follows: [(PhSO2) 2CF-] (20) ≈ PhSO2CCl2 - (32) > PhSO2CHF- (31) > PhSO 2CF2- (30). In the case of fluoroalkylation of aryne (35 as the precursor) and α,β-acetylenic ketones 46 with fluorobis(phenylsulfonyl)methane (21), fluorobis(phenylsulfonyl)methylated arenes 36 and β-fluorobis(phenylsulfonyl)methylated α,β-enones 47 were obtained as the corresponding products in good yields. During the reaction between 2-fluoro-2-(phenylsulfonyl)acetophenone (34) and arynes or activated alkynes 46, an intramolecular tandem reaction process leads to the formation of acyl-fluoroalkylated arenes 43 or α-acyl-β- fluoroalkylated α,β-enones 48. It turned out that the softness of a fluorine-bearing carbanion (such as 20 or 33 derived from 21 or 34) plays a crucial role for the success of the nucleophilic fluoroalkylation reactions with arynes and some activated alkynes (α,β-acetylenic ketones).
