Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles

Benzo[b]heterole represents an important class of heterocycles that is comprised of a variety of functional molecules. For example, indole and benzofuran are ubiquitously present in biologically active natural and unnatural compounds. As such, a number of methods have been developed for their synthe...

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Main Author: Wu, Bin
Other Authors: Yoshikai Naohiko
Format: Theses and Dissertations
Language:English
Published: 2017
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Online Access:http://hdl.handle.net/10356/69464
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-694642023-02-28T23:53:33Z Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles Wu, Bin Yoshikai Naohiko School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis Benzo[b]heterole represents an important class of heterocycles that is comprised of a variety of functional molecules. For example, indole and benzofuran are ubiquitously present in biologically active natural and unnatural compounds. As such, a number of methods have been developed for their synthesis. On the other hand, benzoheteroles containing other Group 13–16 elements are now gaining interested, especially for their unique optical and electronic properties that warrant their applications in various areas including electronics, imaging, and sensing. Nevertheless, synthetic methods for these heterocycles have been relatively limited. This thesis describes the development of new synthetic approaches that enable expedient, modular, and divergent synthesis of benzoheteroles and related heterocycles from readily available starting materials. Our main approach capitalizes on the cobalt-catalyzed "migratory arylzincation" reaction of an alkyne, which affords an ortho-alkenylarylzinc species as a key intermediate. It has been demonstrated that this common intermediate can be readily transformed into several members of the benzoheterole family such as benzothiophene, benzoselenophene, benzotellurophene, and benzophosphole, in a one-pot manner for some cases. Besides benzoheteroles, we have also established a new synthetic route to dibenzoheteroles based on the facile two-step conversion of 2-iodobiaryls into 2,2'-diiodobiaryls via a sequence of oxidative cyclization–iodinative ring opening. Collectively, the new approaches developed in this study have opened access to a diverse set of hitherto inaccessible or difficult-to-access functionalized benzoheteroles and related heterocycles, which may hold promise for applications as functional materials. ​Doctor of Philosophy (SPMS) 2017-01-24T07:43:13Z 2017-01-24T07:43:13Z 2017 Thesis Wu, B. (2017). Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles. Doctoral thesis, Nanyang Technological University, Singapore. http://hdl.handle.net/10356/69464 10.32657/10356/69464 en 266 p. application/pdf
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis
spellingShingle DRNTU::Science::Chemistry::Organic chemistry::Organic synthesis
Wu, Bin
Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
description Benzo[b]heterole represents an important class of heterocycles that is comprised of a variety of functional molecules. For example, indole and benzofuran are ubiquitously present in biologically active natural and unnatural compounds. As such, a number of methods have been developed for their synthesis. On the other hand, benzoheteroles containing other Group 13–16 elements are now gaining interested, especially for their unique optical and electronic properties that warrant their applications in various areas including electronics, imaging, and sensing. Nevertheless, synthetic methods for these heterocycles have been relatively limited. This thesis describes the development of new synthetic approaches that enable expedient, modular, and divergent synthesis of benzoheteroles and related heterocycles from readily available starting materials. Our main approach capitalizes on the cobalt-catalyzed "migratory arylzincation" reaction of an alkyne, which affords an ortho-alkenylarylzinc species as a key intermediate. It has been demonstrated that this common intermediate can be readily transformed into several members of the benzoheterole family such as benzothiophene, benzoselenophene, benzotellurophene, and benzophosphole, in a one-pot manner for some cases. Besides benzoheteroles, we have also established a new synthetic route to dibenzoheteroles based on the facile two-step conversion of 2-iodobiaryls into 2,2'-diiodobiaryls via a sequence of oxidative cyclization–iodinative ring opening. Collectively, the new approaches developed in this study have opened access to a diverse set of hitherto inaccessible or difficult-to-access functionalized benzoheteroles and related heterocycles, which may hold promise for applications as functional materials.
author2 Yoshikai Naohiko
author_facet Yoshikai Naohiko
Wu, Bin
format Theses and Dissertations
author Wu, Bin
author_sort Wu, Bin
title Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
title_short Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
title_full Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
title_fullStr Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
title_full_unstemmed Modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
title_sort modular and diversity-oriented synthetic approaches to benzoheteroles and dibenzoheteroles
publishDate 2017
url http://hdl.handle.net/10356/69464
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