Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions
Summary: 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 me...
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doaj-02957a29a75f4262a6dcd684459f59302020-11-25T03:14:47ZengElsevieriScience2589-00422020-07-01237101307Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free ConditionsHaiwen Wang0Liyun Liang1Zhirong Guo2Hui Peng3Shuang Qiao4Nemai Saha5Daqian Zhu6Wenbin Zeng7Yunyun Chen8Peng Huang9Shijun Wen10State Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, ChinaState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, ChinaState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, ChinaState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, ChinaState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, ChinaBerhampore Girl's College, Berhampore, Murshidabad, West Bengal 742101, IndiaState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, ChinaXiangya School of Pharmaceutical Sciences, Central South University, Changsha 410013, ChinaSchool of Pharmaceutical Science, Sun Yat-sen University, Guangzhou 510006, ChinaState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, China; Corresponding authorState Key Laboratory of Oncology in South China, Collaborative Innovation Center for Cancer Medicine, Sun Yat-sen University Cancer Center, 651 Dongfeng East Road, Guangzhou 510060, China; Corresponding authorSummary: 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.http://www.sciencedirect.com/science/article/pii/S2589004220304946ChemistryCatalysisOrganic ChemistryOrganic Synthesis |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Haiwen Wang Liyun Liang Zhirong Guo Hui Peng Shuang Qiao Nemai Saha Daqian Zhu Wenbin Zeng Yunyun Chen Peng Huang Shijun Wen |
spellingShingle |
Haiwen Wang Liyun Liang Zhirong Guo Hui Peng Shuang Qiao Nemai Saha Daqian Zhu Wenbin Zeng Yunyun Chen Peng Huang Shijun Wen Highly Reactive Cyclic Monoaryl Iodoniums Tuned as Carbene Generators Couple with Nucleophiles under Metal-Free Conditions iScience Chemistry Catalysis Organic Chemistry Organic Synthesis |
author_facet |
Haiwen Wang Liyun Liang Zhirong Guo Hui Peng Shuang Qiao Nemai Saha Daqian Zhu Wenbin Zeng Yunyun Chen Peng Huang Shijun Wen |
author_sort |
Haiwen Wang |
title |
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_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_sort |
highly reactive cyclic monoaryl iodoniums tuned as carbene generators couple with nucleophiles under metal-free conditions |
publisher |
Elsevier |
series |
iScience |
issn |
2589-0042 |
publishDate |
2020-07-01 |
description |
Summary: 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. |
topic |
Chemistry Catalysis Organic Chemistry Organic Synthesis |
url |
http://www.sciencedirect.com/science/article/pii/S2589004220304946 |
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