Novel 10-I-3 hypervalent iodine-based compounds for electrophilic trifluoromethylation
Novel 10-I-3 hypervalent iodine-based compounds for electrophilic trifluoromethylation
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DOI：
10.1002/chem.200501052
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发表时间：
2006-03-08
影响因子：
4.3
通讯作者：
Togni, A
中科院分区：
文献类型：
--
作者：
Eisenberger, P;Gischig, S;Togni, A
合成了一类新的10-1-3高价碘化合物，其中CF 3官能团直接参与高价键。这些材料可通过在亚化学计量量的氟化物存在下使用Me 3SiCF 3在碘处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-苯碘酰-3-（H）-酮和两种取代的1-三氟甲基-1，3-二氢-1，2-苯碘酰）进行X射线晶体学分析，验证了碘处预期的T形几何形状。三氟甲基部分到有机亲核试剂的直接亲电转移的初步结果显示在相对温和的条件下，在极性非质子溶剂中的适度反应性。整个过程可以被理解为CF 3基团的一个正式的umpolung。
The synthesis of a new family of 10-1-3 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-(H)-one and two Substituted l-trifluoromethyl-.1,3-dihydro-1,2-benziodoxoles). Preliminary results for the direct electrophilic transfer of the trifluorormethyl 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.