On the use of triarylsilanols as catalysts for direct amidation of carboxylic acids
File(s)
Published version
Author(s)
Type
Journal Article
Abstract
Triarylsilanols are reported as the first silicon-centred molecular catalysts for direct amidation of carboxylic acids with amines as identified after a screen of silanols, silanediols, disiloxanediols and incompletely condensed silsesquioxanes as potential homogeneous catalysts. Subsequent synthesis and testing of various electronically differentiated triarylsilanols identify tris(p-haloaryl)silanols as more active than the parent triarylsilanol, where the bromide congener was found to be the most active. Catalyst decomposition can be observed by NMR methods, but RPKA methods reveal that product inhibition is operative, where tertiary amides are more inhibitory than secondary amides. Studies using an authentically synthesised triaryl silylester as a putative intermediate in the catalytic system enable a plausible mechanism to be proposed as supported by computations.
Date Issued
2023-07-21
Date Acceptance
2023-06-16
Citation
Journal of Organic Chemistry, 2023, 88 (14), pp.9853-9869
ISSN
0022-3263
Publisher
American Chemical Society
Start Page
9853
End Page
9869
Journal / Book Title
Journal of Organic Chemistry
Volume
88
Issue
14
Copyright Statement
© 2023 The Authors. Published by American Chemical Society. This work is licensed under a Creative Commons Attribution 4.0 International License (https://creativecommons.org/licenses/by/4.0/).
License URL
Identifier
https://pubs.acs.org/doi/10.1021/acs.joc.3c00585
Publication Status
Published
Date Publish Online
2023-07-11