Chemoselective intramolecular functionalization of methyl groups in nonconstrained molecules promoted by
Nieves R Paz1, Dionisio Rodríguez-Sosa1, Haydee Valdés2
1†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
Abstract:
Mechanistic evidence observed in Hofmann-Löffler-Freytag-type reactions has been crucial to achieve the chemoselective functionalization of methyl groups under mild conditions. Radical-mediated methyl iodination and subsequent oxidative deiodination are the key steps in this functionalization, where iodine chemistry has a pivotal role on the formation of the C-N bond. The concepts of single hydrogen atom transfer (SHAT) and multiple hydrogen atom transfer (MHAT) are introduced to describe the observed chemoselectivity.
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