Electrophilic Trifluoromethylation of S-Hydrogen Phosphorothioates

被引：59

作者：

Santschi, Nico ^{[1
]}

Togni, Antonio ^{[1
]}

机构：

[1] ETH, Swiss Fed Inst Technol, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 76卷 / 10期

关键词：

HYPERVALENT; PHOSPHORUS; SECONDARY; ANALOGS; ESTERS; AGENTS;

D O I：

10.1021/jo200522w

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of S-hydrogen phosphorothioates have been converted to the corresponding S-trifluoromethyl derivatives upon reaction with the electrophilic trifluoromethylation reagent 1 (trifluoromethyl 1,3-dihydro-3,3-dimethyl-1,2-benziodoxole). Relative rate data were obtained by F-19 NMR monitoring of competition experiments and were evaluated by means of the Taft equation. A high positive polar sensitivity factor of 2.55 was found for electron-rich substrates and a negative one of -0.37 for electron-poor ones, implying the involvement of two different rate-determining steps. Furthermore, the reaction was found to be unaffected by steric factors.

引用

页码：4189 / 4193

页数：5

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