Cargando…

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...

Descripción completa

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
_version_ 1783333339356200960
author Mowdawalla, Cyrus
Ahmed, Faiz
Li, Tian
Pham, Kiet
Dave, Loma
Kim, Grace
Hyatt, I F Dempsey
author_facet Mowdawalla, Cyrus
Ahmed, Faiz
Li, Tian
Pham, Kiet
Dave, Loma
Kim, Grace
Hyatt, I F Dempsey
author_sort Mowdawalla, Cyrus
collection PubMed
description 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).
format Online
Article
Text
id pubmed-6009249
institution National Center for Biotechnology Information
language English
publishDate 2018
publisher Beilstein-Institut
record_format MEDLINE/PubMed
spelling pubmed-60092492018-07-05 Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups Mowdawalla, Cyrus Ahmed, Faiz Li, Tian Pham, Kiet Dave, Loma Kim, Grace Hyatt, I F Dempsey Beilstein J Org Chem Full Research Paper 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). Beilstein-Institut 2018-05-14 /pmc/articles/PMC6009249/ /pubmed/29977377 http://dx.doi.org/10.3762/bjoc.14.91 Text en Copyright © 2018, Mowdawalla et al. https://creativecommons.org/licenses/by/4.0https://www.beilstein-journals.org/bjoc/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms)
spellingShingle Full Research Paper
Mowdawalla, Cyrus
Ahmed, Faiz
Li, Tian
Pham, Kiet
Dave, Loma
Kim, Grace
Hyatt, I F Dempsey
Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
title Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
title_full Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
title_fullStr Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
title_full_unstemmed Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
title_short Hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
title_sort hypervalent iodine-guided electrophilic substitution: para-selective substitution across aryl iodonium compounds with benzyl groups
topic Full Research Paper
url 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
work_keys_str_mv AT mowdawallacyrus hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups
AT ahmedfaiz hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups
AT litian hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups
AT phamkiet hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups
AT daveloma hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups
AT kimgrace hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups
AT hyattifdempsey hypervalentiodineguidedelectrophilicsubstitutionparaselectivesubstitutionacrossaryliodoniumcompoundswithbenzylgroups