16029-98-4 / 三甲基碘硅烷脫甲基反應(yīng)

三甲基碘硅烷脫甲基是通過芳基甲醚與三甲基碘硅烷生成芳基硅醚，水解得到脫甲基產(chǎn)物。一種常用的去甲基試劑，在此體系中，雙鍵、三鍵、酮羰基、氨基和鹵代物穩(wěn)定，但芐醚、三苯甲基醚、叔丁基醚不穩(wěn)定。三甲基碘硅烷能裂解酯但比醚慢。

反應(yīng)機(jī)理

由于氧與硅的結(jié)合能力較強(qiáng)，容易形成氧鎓離子，碘離子親核取代生成芳基硅醚，水解得到產(chǎn)物。

反應(yīng)實(shí)例

【J. Chem. Res.,2009,4 ,229- 230.】

General Procedure forDealkylation of Ether. To a 2 M solution of ether (1 equiv.) in a suitable solvent (Table 10) is added neattrimethylsilyl iodide (1.3 equiv.) through a dry syringe. The reaction is maintained at temperature indicated in Table 10 and monitored by NMR forcompletion. Yields are calculated by NMR integration of pertinent peaks. Forisolation of the alcohols, at the completion of the reaction, the excesstrimethylsilyl iodide is destroyed and the intermediate trimethylsilyl etherformed during the reaction is hydrolyzed to alcohol by pouring the reactionmixture into methanol (4 equiv.). The volatile components are removed atreduced pressure and the residue is taken up in ether, washed with aqueoussodium bisulfite, aqueous sodium bicarbonate and brine and dried. The residueleft after evaporation of solvent is further purified (if necessary) by columnchromatography on silica gel.

【M. E. Jung and M. A.Lyster, J. Org. Chem., 1977, 42, 3761】