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Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes

An efficient Ag/pyridine co-mediated oxidative arylthiocyanation of activated alkenes via radical addition/cyclization cascade process was developed. This reaction could be carried out under mild conditions to provide biologically interesting 3-alkylthiocyanato-2-oxindoles in good to excellent yield...

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Autores principales: Kong, De-Long, Du, Jian-Xun, Chu, Wei-Ming, Ma, Chun-Ying, Tao, Jia-Yi, Feng, Wen-Hua
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6222345/
https://www.ncbi.nlm.nih.gov/pubmed/30360416
http://dx.doi.org/10.3390/molecules23102727
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author Kong, De-Long
Du, Jian-Xun
Chu, Wei-Ming
Ma, Chun-Ying
Tao, Jia-Yi
Feng, Wen-Hua
author_facet Kong, De-Long
Du, Jian-Xun
Chu, Wei-Ming
Ma, Chun-Ying
Tao, Jia-Yi
Feng, Wen-Hua
author_sort Kong, De-Long
collection PubMed
description An efficient Ag/pyridine co-mediated oxidative arylthiocyanation of activated alkenes via radical addition/cyclization cascade process was developed. This reaction could be carried out under mild conditions to provide biologically interesting 3-alkylthiocyanato-2-oxindoles in good to excellent yields. Mechanistic studies suggested a unique NCS• radical addition path and clarified the dual roles of catalytic pyridine as base and crucial ligand to accelerate the oxidation of Ag(I) to Ag(II), which is likely oxidant responsible for the formation of NCS• radical. These mechanistic results may impact the design and refinement of other radical based reactions proceeding through catalytic oxidations mediated by Ag(I)-pyridine/persulfate. The chemical versatility of thiocyanate moiety was also highlighted via SCN-tailoring chemistry in post-synthetic transformation for new S-C(sp(3)/sp(2)/sp), S-P, and S-S bonds constructions. The protocol provides an easy access to many important bioisosteres in medicinal chemistry and an array of sulfur-containing 2-oxindoles that are difficult to prepare by other approaches.
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spelling pubmed-62223452018-11-13 Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes Kong, De-Long Du, Jian-Xun Chu, Wei-Ming Ma, Chun-Ying Tao, Jia-Yi Feng, Wen-Hua Molecules Article An efficient Ag/pyridine co-mediated oxidative arylthiocyanation of activated alkenes via radical addition/cyclization cascade process was developed. This reaction could be carried out under mild conditions to provide biologically interesting 3-alkylthiocyanato-2-oxindoles in good to excellent yields. Mechanistic studies suggested a unique NCS• radical addition path and clarified the dual roles of catalytic pyridine as base and crucial ligand to accelerate the oxidation of Ag(I) to Ag(II), which is likely oxidant responsible for the formation of NCS• radical. These mechanistic results may impact the design and refinement of other radical based reactions proceeding through catalytic oxidations mediated by Ag(I)-pyridine/persulfate. The chemical versatility of thiocyanate moiety was also highlighted via SCN-tailoring chemistry in post-synthetic transformation for new S-C(sp(3)/sp(2)/sp), S-P, and S-S bonds constructions. The protocol provides an easy access to many important bioisosteres in medicinal chemistry and an array of sulfur-containing 2-oxindoles that are difficult to prepare by other approaches. MDPI 2018-10-22 /pmc/articles/PMC6222345/ /pubmed/30360416 http://dx.doi.org/10.3390/molecules23102727 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Kong, De-Long
Du, Jian-Xun
Chu, Wei-Ming
Ma, Chun-Ying
Tao, Jia-Yi
Feng, Wen-Hua
Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes
title Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes
title_full Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes
title_fullStr Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes
title_full_unstemmed Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes
title_short Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes
title_sort ag/pyridine co-mediated oxidative arylthiocyanation of activated alkenes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6222345/
https://www.ncbi.nlm.nih.gov/pubmed/30360416
http://dx.doi.org/10.3390/molecules23102727
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