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- Title
Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents.
- Authors
Zhang, Jingjing; Yang, Jin‐Dong; Zheng, Hanliang; Xue, Xiao‐Song; Mayr, Herbert; Cheng, Jin‐Pei
- Abstract
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.
- Subjects
CHEMICAL reagents; ELECTROPHILES; CHEMICAL reactions; CHEMICAL testing; CRYSTAL structure
- Publication
Angewandte Chemie, 2018, Vol 130, Issue 39, p12872
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201805859