Cargando…

A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes

Although great success has been achieved in selective C–C bond cleavage via the intramolecular radical remote migration process of several carbon-based groups, the development of the radical-based remote vinyl migration process remains a formidable challenge because of the energetically unfavorable...

Descripción completa

Detalles Bibliográficos
Autores principales: Li, Lei, Li, Zhong-Liang, Gu, Qiang-Shuai, Wang, Na, Liu, Xin-Yuan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Association for the Advancement of Science 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5669612/
https://www.ncbi.nlm.nih.gov/pubmed/29119139
http://dx.doi.org/10.1126/sciadv.1701487
_version_ 1783275872544882688
author Li, Lei
Li, Zhong-Liang
Gu, Qiang-Shuai
Wang, Na
Liu, Xin-Yuan
author_facet Li, Lei
Li, Zhong-Liang
Gu, Qiang-Shuai
Wang, Na
Liu, Xin-Yuan
author_sort Li, Lei
collection PubMed
description Although great success has been achieved in selective C–C bond cleavage via the intramolecular radical remote migration process of several carbon-based groups, the development of the radical-based remote vinyl migration process remains a formidable challenge because of the energetically unfavorable process. To address this problem, we report here, for the first time, a novel C–C bond reorganization strategy via an unprecedented radical 1,3-, 1,4-, or 1,5-vinyl migration triggered by various types of fluoroalkylation of alkenes for the efficient realization of 1,2-fluoroalkylalkenylation reaction. This strategy provides an expedient and broadly applicable platform to access skeletally and functionally diverse fluoroalkyl-containing medium- and large-sized cyclic alkenes with excellent chemo-, regio-, and stereoselectivity. The broad substrate scope, which covers distinctly electron-neutral or electron-deficient alkenyl migrating groups and various fluoroalkyl radical precursors, the excellent functional group tolerance, the remarkable selectivity, and the operational simplicity, as well as versatile transformations of the products, make this approach practical and attractive.
format Online
Article
Text
id pubmed-5669612
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher American Association for the Advancement of Science
record_format MEDLINE/PubMed
spelling pubmed-56696122017-11-08 A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes Li, Lei Li, Zhong-Liang Gu, Qiang-Shuai Wang, Na Liu, Xin-Yuan Sci Adv Research Articles Although great success has been achieved in selective C–C bond cleavage via the intramolecular radical remote migration process of several carbon-based groups, the development of the radical-based remote vinyl migration process remains a formidable challenge because of the energetically unfavorable process. To address this problem, we report here, for the first time, a novel C–C bond reorganization strategy via an unprecedented radical 1,3-, 1,4-, or 1,5-vinyl migration triggered by various types of fluoroalkylation of alkenes for the efficient realization of 1,2-fluoroalkylalkenylation reaction. This strategy provides an expedient and broadly applicable platform to access skeletally and functionally diverse fluoroalkyl-containing medium- and large-sized cyclic alkenes with excellent chemo-, regio-, and stereoselectivity. The broad substrate scope, which covers distinctly electron-neutral or electron-deficient alkenyl migrating groups and various fluoroalkyl radical precursors, the excellent functional group tolerance, the remarkable selectivity, and the operational simplicity, as well as versatile transformations of the products, make this approach practical and attractive. American Association for the Advancement of Science 2017-11-03 /pmc/articles/PMC5669612/ /pubmed/29119139 http://dx.doi.org/10.1126/sciadv.1701487 Text en Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC). http://creativecommons.org/licenses/by-nc/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license (http://creativecommons.org/licenses/by-nc/4.0/) , which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.
spellingShingle Research Articles
Li, Lei
Li, Zhong-Liang
Gu, Qiang-Shuai
Wang, Na
Liu, Xin-Yuan
A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
title A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
title_full A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
title_fullStr A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
title_full_unstemmed A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
title_short A remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
title_sort remote c–c bond cleavage–enabled skeletal reorganization: access to medium-/large-sized cyclic alkenes
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5669612/
https://www.ncbi.nlm.nih.gov/pubmed/29119139
http://dx.doi.org/10.1126/sciadv.1701487
work_keys_str_mv AT lilei aremoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT lizhongliang aremoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT guqiangshuai aremoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT wangna aremoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT liuxinyuan aremoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT lilei remoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT lizhongliang remoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT guqiangshuai remoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT wangna remoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes
AT liuxinyuan remoteccbondcleavageenabledskeletalreorganizationaccesstomediumlargesizedcyclicalkenes