Cargando…
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...
Autores principales: | , , , , , , , , , , |
---|---|
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 |
_version_ | 1783554757611225088 |
---|---|
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. |
format | Online Article Text |
id | pubmed-7338778 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Elsevier |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT wanghaiwen highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT liangliyun highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT guozhirong highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT penghui highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT qiaoshuang highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT sahanemai highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT zhudaqian highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT zengwenbin highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT chenyunyun highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT huangpeng highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions AT wenshijun highlyreactivecyclicmonoaryliodoniumstunedascarbenegeneratorscouplewithnucleophilesundermetalfreeconditions |