Eisenberger Patrick, Gischig Sebastian, Togni Antonio
Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Hönggerberg, 8093 Zürich, Switzerland.
Chemistry. 2006 Mar 8;12(9):2579-86. doi: 10.1002/chem.200501052.
The synthesis of a new family of 10-I-3 hypervalent iodine compounds is described in which the CF3 functionality participates directly in the hypervalent bond. These materials are accessible by nucleophilic ligand substitution at iodine using Me3SiCF3 in the presence of a substoichiometric amount of fluoride. The expected T-shaped geometry at iodine was verified by X-ray crystallographic analyses of three of the products (1-trifluoromethyl-1,2-benziodoxol-3-(1 H)-one and two substituted 1-trifluoromethyl-1,3-dihydro-1,2-benziodoxoles). Preliminary results for the direct electrophilic transfer of the trifluoromethyl moiety onto organic nucleophiles show modest reactivity in polar aprotic solvents under relatively mild conditions. The overall process can be understood as a formal umpolung of the CF3 group.
描述了一个新的10-I-3高价碘化合物家族的合成，其中CF3官能团直接参与高价键。这些材料可通过在化学计量以下的氟化物存在下，使用Me3SiCF3对碘进行亲核配体取代来获得。通过对三种产物（1-三氟甲基-1,2-苯并碘氧杂环戊-3-(1H)-酮和两种取代的1-三氟甲基-1,3-二氢-1,2-苯并碘氧杂环戊烷）的X射线晶体学分析，证实了碘处预期的T形几何结构。三氟甲基部分直接亲电转移到有机亲核试剂上的初步结果表明，在相对温和的条件下，在极性非质子溶剂中具有适度的反应活性。整个过程可以理解为CF3基团的形式反转。
