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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...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Beilstein-Institut
2018
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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 |
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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 |
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