Chemoselective intramolecular functionalization of methyl groups in nonconstrained molecules promoted by N-iodosulfonamides.
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.
†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
Nieves R
NR
Paz
†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
Dionisio
D
Rodríguez-Sosa
§Departamento de Física Teórica, Atómica y Óptica, Universidad de Valladolid, Paseo de Belén 7, 47011 Valladolid, Spain.
Haydee
H
Valdés
†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
Ricardo
R
Marticorena
‡Departamento de Química Orgánica, Universidad de La Laguna, Av. Astrofísico Francisco Sánchez s/n, 38206 La Laguna, Tenerife, Spain.
Daniel
D
Melián
†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
M Belén
MB
Copano
†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
Concepción C
CC
González
†Instituto de Productos Naturales y Agrobiología C.S.I.C., Av. Astrofísico Francisco Sánchez 3, 38206 La Laguna, Tenerife, Spain.
Antonio J
AJ
Herrera