- Nonconventional difluoroalkylation of C(sp2)-H bonds through hydroarylation
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An unprecedented Rh-catalyzed C2-difluoroalkylation of indole derivatives with 2,2-difluorovinyl arenesulfonates has been reported. This reaction provides a rare instance of catalytic difluoroalkylation through hydroarylation of gem-difluoroalkenes. The sulfonate group works as a chelating ligand, thus stabilizing the rhodacycle intermediate, leading to the uncommon transformation.
- Zhu, Chuan,Song, Shengjin,Zhou, Lu,Wang, Ding-Xing,Feng, Chao,Loh, Teck-Peng
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supporting information
p. 9482 - 9485
(2017/09/01)
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- The SN3-SN2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols
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Rate constants for a wide range of binary aqueous mixtures and product selectivities (S) in ethanol - Water (EW) and methanol-water (MW) mixtures, are reported at 25 °C for solvolyses of benzenesulfonyl chloride and the 4-chloro - Derivative. S is defined as follows using molar concentrations: S =([ester product]/[acid product]) × ([water solvent]/[alcohol solvent]). Additional selectivity data are reported for solvolyses of 4-Z-substituted sulfonyl chlorides (Z - OMe, Me, H, Cl and NO2) in 2, 2, 2-trifluoroethanol-water. To explain these results and previously published data on kinetic solvent isotope effects (KSIEs) and on other solvolyses of 4-nitro and 4-methoxybenzenesulfonyl chloride, a mechanistic spectrum involving a change from third order to second order is proposed. The molecularity of these reactions is discussed, along with new term 'SN3-SN2 spectrum' and its connection with the better established term 'S N2-SN1 spectrum'. Copyright
- Bentley, T. William,Jones, Robert O,Kang, Dae Ho,Koo, Sun
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scheme or table
p. 799 - 806
(2010/06/16)
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