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Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions

Cross-coupling reactions between aryl iodide and nucleophiles have been well developed. Iodoniums equipped with a reactive C-I(III) bond accelerate cross-coupling reactions of aryl iodide. Among them, cyclic diaryliodoniums are more atom economical; however; they are often in the trap of metal relia...

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Autores principales: Wang, Haiwen, Liang, Liyun, Guo, Zhirong, Peng, Hui, Qiao, Shuang, Saha, Nemai, Zhu, Daqian, Zeng, Wenbin, Chen, Yunyun, Huang, Peng, Wen, Shijun
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Elsevier 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7338778/
https://www.ncbi.nlm.nih.gov/pubmed/32634743
http://dx.doi.org/10.1016/j.isci.2020.101307
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author Wang, Haiwen
Liang, Liyun
Guo, Zhirong
Peng, Hui
Qiao, Shuang
Saha, Nemai
Zhu, Daqian
Zeng, Wenbin
Chen, Yunyun
Huang, Peng
Wen, Shijun
author_facet Wang, Haiwen
Liang, Liyun
Guo, Zhirong
Peng, Hui
Qiao, Shuang
Saha, Nemai
Zhu, Daqian
Zeng, Wenbin
Chen, Yunyun
Huang, Peng
Wen, Shijun
author_sort Wang, Haiwen
collection PubMed
description Cross-coupling reactions between aryl iodide and nucleophiles have been well developed. Iodoniums equipped with a reactive C-I(III) bond accelerate cross-coupling reactions of aryl iodide. Among them, cyclic diaryliodoniums are more atom economical; however; they are often in the trap of metal reliance and encounter regioselectivity issues. Now, we have developed a series of highly reactive cyclic monoaryl-vinyl iodoniums that can be tuned to construct C-N, C-O, and C-C bonds without metal catalysis. Under promotion of triethylamine, coupling reactions with aniline, phenol, aromatic acid, and indole proceed rapidly and regioselectively at room temperature. The carbene species is conceptualized as a key intermediate in our mechanism model. Furthermore, the coupling products enable diversity-oriented synthesis strategy to further build up a chemical library of diverse heterocyclic fragments that are in demand in the drug discovery field. Our current work provides a deep insight into the synthetic application of these highly reactive cyclic iodoniums.
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spelling pubmed-73387782020-07-14 Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions Wang, Haiwen Liang, Liyun Guo, Zhirong Peng, Hui Qiao, Shuang Saha, Nemai Zhu, Daqian Zeng, Wenbin Chen, Yunyun Huang, Peng Wen, Shijun iScience Article Cross-coupling reactions between aryl iodide and nucleophiles have been well developed. Iodoniums equipped with a reactive C-I(III) bond accelerate cross-coupling reactions of aryl iodide. Among them, cyclic diaryliodoniums are more atom economical; however; they are often in the trap of metal reliance and encounter regioselectivity issues. Now, we have developed a series of highly reactive cyclic monoaryl-vinyl iodoniums that can be tuned to construct C-N, C-O, and C-C bonds without metal catalysis. Under promotion of triethylamine, coupling reactions with aniline, phenol, aromatic acid, and indole proceed rapidly and regioselectively at room temperature. The carbene species is conceptualized as a key intermediate in our mechanism model. Furthermore, the coupling products enable diversity-oriented synthesis strategy to further build up a chemical library of diverse heterocyclic fragments that are in demand in the drug discovery field. Our current work provides a deep insight into the synthetic application of these highly reactive cyclic iodoniums. Elsevier 2020-06-23 /pmc/articles/PMC7338778/ /pubmed/32634743 http://dx.doi.org/10.1016/j.isci.2020.101307 Text en © 2020 The Authors http://creativecommons.org/licenses/by-nc-nd/4.0/ This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Article
Wang, Haiwen
Liang, Liyun
Guo, Zhirong
Peng, Hui
Qiao, Shuang
Saha, Nemai
Zhu, Daqian
Zeng, Wenbin
Chen, Yunyun
Huang, Peng
Wen, Shijun
Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
title Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
title_full Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
title_fullStr Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
title_full_unstemmed Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
title_short Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
title_sort highly reactive cyclic monoaryl iodoniums tuned as carbene generators couple with nucleophiles under metal-free conditions
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7338778/
https://www.ncbi.nlm.nih.gov/pubmed/32634743
http://dx.doi.org/10.1016/j.isci.2020.101307
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