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Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates

Derek Barbee, Andrew Barron

Phosphorus, Sulfur, and Silicon and the Related Elements, Volume: 195, Issue: 3, Pages: 231 - 244

Swansea University Author: Andrew Barron

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DOI (Published version): 10.1080/10426507.2019.1673750

Abstract

The development of novel multi-substituted aryl-phosphonate compounds offers promise as new building blocks for metal-organic frameworks (MOFs) materials with excellent properties in regards to porosity and gas sorption. We demonstrate the efficiency of the palladium-catalyzed Hirao cross-coupling r...

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Published in: Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 1563-5325
Published: Informa UK Limited 2020
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URI: https://cronfa.swan.ac.uk/Record/cronfa53135
first_indexed 2020-01-07T19:46:45Z
last_indexed 2023-01-11T14:30:37Z
id cronfa53135
recordtype SURis
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spelling 2022-11-02T12:44:09.9925949 v2 53135 2020-01-07 Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates 92e452f20936d688d36f91c78574241d Andrew Barron Andrew Barron true false 2020-01-07 The development of novel multi-substituted aryl-phosphonate compounds offers promise as new building blocks for metal-organic frameworks (MOFs) materials with excellent properties in regards to porosity and gas sorption. We demonstrate the efficiency of the palladium-catalyzed Hirao cross-coupling reaction in the synthesis of substituted phosphonates; however, attempts to prepare derivatives with isoretical expansion through the cyclization of 4-(4′-bromophenyl)acetophenone resulted in an extremely low yield, with the isolation of the dimer intermediate. Ab initio calculations showed that while the trimerization of acetophenone is exothermic, that of 4-phenyl acetophenone is endothermic. By contrast, the cyclization of 4-(4′-bromophenyl)benzonitrile is exothermic and allows for the formation of the appropriate phosphonic acid. The benzonitrile methodology also allows for the formation of ortho methyl derivatives with high steric hindrance. All the multi-substituted aryl-phosphonate compounds reported herein can be prepared on a multi gram scale enabling researchers a wider range of building blocks for phosphonate MOFs. Journal Article Phosphorus, Sulfur, and Silicon and the Related Elements 195 3 231 244 Informa UK Limited 1042-6507 1563-5325 Aryl-phosphonate; coupling; palladium; catalyst 3 3 2020 2020-03-03 10.1080/10426507.2019.1673750 COLLEGE NANME COLLEGE CODE Swansea University 2022-11-02T12:44:09.9925949 2020-01-07T14:32:05.4733005 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Derek Barbee 1 Andrew Barron 2
title Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
spellingShingle Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
Andrew Barron
title_short Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
title_full Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
title_fullStr Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
title_full_unstemmed Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
title_sort Scalable synthesis of multi-substituted aryl-phosphonates: Exploring the limits of isoretical expansion and the synthesis of new triazene-based phosphonates
author_id_str_mv 92e452f20936d688d36f91c78574241d
author_id_fullname_str_mv 92e452f20936d688d36f91c78574241d_***_Andrew Barron
author Andrew Barron
author2 Derek Barbee
Andrew Barron
format Journal article
container_title Phosphorus, Sulfur, and Silicon and the Related Elements
container_volume 195
container_issue 3
container_start_page 231
publishDate 2020
institution Swansea University
issn 1042-6507
1563-5325
doi_str_mv 10.1080/10426507.2019.1673750
publisher Informa UK Limited
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
document_store_str 0
active_str 0
description The development of novel multi-substituted aryl-phosphonate compounds offers promise as new building blocks for metal-organic frameworks (MOFs) materials with excellent properties in regards to porosity and gas sorption. We demonstrate the efficiency of the palladium-catalyzed Hirao cross-coupling reaction in the synthesis of substituted phosphonates; however, attempts to prepare derivatives with isoretical expansion through the cyclization of 4-(4′-bromophenyl)acetophenone resulted in an extremely low yield, with the isolation of the dimer intermediate. Ab initio calculations showed that while the trimerization of acetophenone is exothermic, that of 4-phenyl acetophenone is endothermic. By contrast, the cyclization of 4-(4′-bromophenyl)benzonitrile is exothermic and allows for the formation of the appropriate phosphonic acid. The benzonitrile methodology also allows for the formation of ortho methyl derivatives with high steric hindrance. All the multi-substituted aryl-phosphonate compounds reported herein can be prepared on a multi gram scale enabling researchers a wider range of building blocks for phosphonate MOFs.
published_date 2020-03-03T07:41:24Z
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score 11.0583515

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