Imperial College London
Professor Henry S. Rzepa

Professor Henry S. Rzepa

Faculty of Natural Sciences, Department of Chemistry

Emeritus Professor of Computational Chemistry
 
 
 
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Contact

 

+44 (0)7514 623 653h.rzepa Website

 
 
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Location

 

501AMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Braddock:2023:10.1021/acs.joc.3c00585,
author = {Braddock, D and Rowley, B and Lickiss, P and Fussell, S and Qamar, R and Pugh, D and Rzepa, H and White, A},
doi = {10.1021/acs.joc.3c00585},
journal = {Journal of Organic Chemistry},
pages = {9853--9869},
title = {On the use of triarylsilanols as catalysts for direct amidation of carboxylic acids},
url = {http://dx.doi.org/10.1021/acs.joc.3c00585},
volume = {88},
year = {2023}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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.
AU  - Braddock,D
AU  - Rowley,B
AU  - Lickiss,P
AU  - Fussell,S
AU  - Qamar,R
AU  - Pugh,D
AU  - Rzepa,H
AU  - White,A
DO  - 10.1021/acs.joc.3c00585
EP  - 9869
PY  - 2023///
SN  - 0022-3263
SP  - 9853
TI  - On the use of triarylsilanols as catalysts for direct amidation of carboxylic acids
T2  - Journal of Organic Chemistry
UR  - http://dx.doi.org/10.1021/acs.joc.3c00585
UR  - https://pubs.acs.org/doi/10.1021/acs.joc.3c00585
UR  - http://hdl.handle.net/10044/1/105027
VL  - 88
ER  -
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