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Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups

The reactivity of benzyl hypervalent iodine intermediates was explored in congruence with the reductive iodonio-Claisen rearrangement (RICR) to show that there may be an underlying mechanism which expands the reasoning behind the previously known C–C bond-forming reaction. By rationalizing the hyper...

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Detalles Bibliográficos
Autores principales: Mowdawalla, Cyrus, Ahmed, Faiz, Li, Tian, Pham, Kiet, Dave, Loma, Kim, Grace, Hyatt, I F Dempsey
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6009249/
https://www.ncbi.nlm.nih.gov/pubmed/29977377
http://dx.doi.org/10.3762/bjoc.14.91
Descripción
Sumario:The reactivity of benzyl hypervalent iodine intermediates was explored in congruence with the reductive iodonio-Claisen rearrangement (RICR) to show that there may be an underlying mechanism which expands the reasoning behind the previously known C–C bond-forming reaction. By rationalizing the hypervalent iodine’s metal-like properties it was concluded that a transmetallation mechanism could be occurring with metalloid groups such as silicon and boron. Hypervalent iodine reagents such as Zefirov’s reagent, cyclic iodonium reagents, iodosobenzene/BF(3), and PhI(OAc)(2)/BF(3) or triflate-based activators were tested. A desirable facet of the reported reaction is that iodine(I) is incorporated into the product thus providing greater atom economy and a valuable functional group handle for further transformations. The altering of the RICR’s ortho-selectivity to form para-selective products with benzyl hypervalent iodine intermediates suggests a mechanism that involves hypervalent iodine-guided electrophilic substitution (HIGES).