183267-04-1Relevant articles and documents
Preparation and reactivity of tris(trifluoromethylselanyl)carbenium |(CF3Se)3C+l and trifluromethylsulfanylacetic acid derivates [CF3S3-nCXn(O)R]
Haas, Alois,Moeller, Guido
, p. 1383 - 1388 (1996)
Reaction pathways for the synthesis of the (CF3E)3C moieties (E = Se, S) are described. [(CF3Se)3C+HAsF6-] was found to be a suitable synthon for the preparation of (CF3Se)3C derivatives. It can be prepared either from (CF3Se)4C or (CF3Se)3CF and AsF5 in liquid SO2. Direct access to (CF3Se)3CF was realized by the reaction of FCBr3 with Hg(SeCF3)2. Treatment of [(CF3Se)3C+][AsF6-] with potassium halides provided (CF3Se)3CX (X = F, Cl, Br). A different course took the reaction with KI, as CF3SeSeCF3 and (CF3Se)2C=C(SeCF3)2 were formed as main products. Minor amounts of (CF3Se)3CC(SeCF3)3 were formed which could be isolated and unambiguously characterized. Only two routes led to a threefold CF3S-substituted acetic acid ester (CF3S)3CC(O)OR [R= CH3, (CH3)3C]: Metatheses between (CF3S)2CBrC(O)OCH3 and Hg(SCF3)2 and metalation of (CF3S)2CHC(O)OR [R = CH3, (CH3)3C] with NaH followed by reaction with CF3SCL. Other precursors such as (CF3S)2CXC(O)OR′ [X = H, Br; R′ = Me3Si, (n-C4H9)3Sn] and (CF3S)2CBrC(O)Y (Y = Cl, Br) were synthesized but could not be converted to the corresponding (CF3S)3C derivatives. Attempts to hydrolyze (CF3S)3CC(O)OR to (CF3S)3CC(O)OH failed. VCH Verlagsgesellschaft mbH, 1996.
Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents
Zhang, Jingjing,Yang, Jin-Dong,Zheng, Hanliang,Xue, Xiao-Song,Mayr, Herbert,Cheng, Jin-Pei
supporting information, p. 12690 - 12695 (2018/09/25)
The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free-energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido-derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X?SCF3 bonds (Tt+DA), the cumol-derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O?S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis.
A conjugate Lewis base-Br?nsted acid catalyst for the sulfenylation of nitrogen containing heterocycles under mild conditions
Nalbandian, Christopher J.,Miller, Eric M.,Toenjes, Sean T.,Gustafson, Jeffery L.
supporting information, p. 1494 - 1497 (2017/02/05)
Catalysts that contain a thiourea tethered to a carboxylic acid were found to affect the sulfenylation of indoles and other N-heterocycles on the hour time scale at room temperature. The mild nature of these conditions allowed for the incorporation of diverse functionalities into more complex heterocycles.