Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones

A binary hybrid system comprising a hypervalent iodine(III) reagent and BF(3)•OEt(2) Lewis acid was found to be effective for the diastereoselective α-acetoxylation of cyclic ketones. In this hybrid system, BF(3)•OEt(2) Lewis acid allowed the activation of the hypervalent iodine(III) reagent and cyc...

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Autores principales: Tan, Jiashen, Zhu, Weiqin, Xu, Weiping, Jing, Yaru, Ke, Zhuofeng, Liu, Yan, Maruoka, Keiji
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2020
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7365914/
https://www.ncbi.nlm.nih.gov/pubmed/32754572
http://dx.doi.org/10.3389/fchem.2020.00467
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author Tan, Jiashen
Zhu, Weiqin
Xu, Weiping
Jing, Yaru
Ke, Zhuofeng
Liu, Yan
Maruoka, Keiji
author_facet Tan, Jiashen
Zhu, Weiqin
Xu, Weiping
Jing, Yaru
Ke, Zhuofeng
Liu, Yan
Maruoka, Keiji
author_sort Tan, Jiashen
collection PubMed
description A binary hybrid system comprising a hypervalent iodine(III) reagent and BF(3)•OEt(2) Lewis acid was found to be effective for the diastereoselective α-acetoxylation of cyclic ketones. In this hybrid system, BF(3)•OEt(2) Lewis acid allowed the activation of the hypervalent iodine(III) reagent and cyclic ketones for smooth α-acetoxylation reaction, achieving high diastereoselectivity. This hypervalent iodine-mediated α-acetoxylation of the cyclic ketone reaction plausibly undergoes an S(N)2 substitution mechanism via an α-C-bound hypervalent iodine intermediate. The diastereoselectivity of the reaction mainly originates from thermodynamic control.
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spelling pubmed-73659142020-08-03 Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones Tan, Jiashen Zhu, Weiqin Xu, Weiping Jing, Yaru Ke, Zhuofeng Liu, Yan Maruoka, Keiji Front Chem Chemistry A binary hybrid system comprising a hypervalent iodine(III) reagent and BF(3)•OEt(2) Lewis acid was found to be effective for the diastereoselective α-acetoxylation of cyclic ketones. In this hybrid system, BF(3)•OEt(2) Lewis acid allowed the activation of the hypervalent iodine(III) reagent and cyclic ketones for smooth α-acetoxylation reaction, achieving high diastereoselectivity. This hypervalent iodine-mediated α-acetoxylation of the cyclic ketone reaction plausibly undergoes an S(N)2 substitution mechanism via an α-C-bound hypervalent iodine intermediate. The diastereoselectivity of the reaction mainly originates from thermodynamic control. Frontiers Media S.A. 2020-07-10 /pmc/articles/PMC7365914/ /pubmed/32754572 http://dx.doi.org/10.3389/fchem.2020.00467 Text en Copyright © 2020 Tan, Zhu, Xu, Jing, Ke, Liu and Maruoka. http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
Tan, Jiashen
Zhu, Weiqin
Xu, Weiping
Jing, Yaru
Ke, Zhuofeng
Liu, Yan
Maruoka, Keiji
Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones
title Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones
title_full Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones
title_fullStr Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones
title_full_unstemmed Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones
title_short Hypervalent Iodine-Mediated Diastereoselective α-Acetoxylation of Cyclic Ketones
title_sort hypervalent iodine-mediated diastereoselective α-acetoxylation of cyclic ketones
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7365914/
https://www.ncbi.nlm.nih.gov/pubmed/32754572
http://dx.doi.org/10.3389/fchem.2020.00467
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