Harnessing Deep Eutectic Solvents for Regioselective Polar Additions to α,β Unsaturated Ketones and Aldehydes
Platten, Andrew W. J. ; Manasi, Iva ; Campana, Mario ; Edler, Karen J. LU
and Hevia, Eva
(2025)
In ChemSusChem
- Abstract
- Advancing the use of air-sensitive polar organometallic Grignard and organolithium reagents under more environmentally benign conditions, here we report the addition of these reagents to a-b unsaturated ketones and aldehydes using the deep eutetic solvent (DES) choline chloride (ChCl): glycerol (Gly) (1:2), under air. Reactions occur at room temperature within seconds with excellent regioselective control. Furthering understanding of how these C-C bond forming processes take place in these reaction media, we have explored the surface concentration of the organic substrate (chalcone) in DES using interfacial tension and neutron reflectivity measurements, finding that chalcone is concentrated at the DES-hydrocarbon interface compared to the... (More)
- Advancing the use of air-sensitive polar organometallic Grignard and organolithium reagents under more environmentally benign conditions, here we report the addition of these reagents to a-b unsaturated ketones and aldehydes using the deep eutetic solvent (DES) choline chloride (ChCl): glycerol (Gly) (1:2), under air. Reactions occur at room temperature within seconds with excellent regioselective control. Furthering understanding of how these C-C bond forming processes take place in these reaction media, we have explored the surface concentration of the organic substrate (chalcone) in DES using interfacial tension and neutron reflectivity measurements, finding that chalcone is concentrated at the DES-hydrocarbon interface compared to the bulk concentration, although the interfacial chalcone concentration is still relatively low in this system. The influence of aggregation of the organometallic reagent in the organic solvent employed has also been evaluated, revealing the importance of achieving a balance between activation (via de-aggregation) and stability (to avoid its decomposition in the DES). This DES approach has been successfully extended to double additions to a-b unsaturated estes and for one pot sequential 1,4 and 1,2 additions to ketones, providing a new entry point to a range of tertiary-alcohols, minimising the use of organic solvents and avoiding intermediate time-consuming purification steps. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/5270ca30-53e7-4ca2-84be-04a36817ffc6
- author
- Platten, Andrew W. J.
; Manasi, Iva
; Campana, Mario
; Edler, Karen J.
LU
and Hevia, Eva
- organization
- publishing date
- 2025-04-01
- type
- Contribution to journal
- publication status
- published
- subject
- in
- ChemSusChem
- article number
- e202402083
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- pmid:39555980
- scopus:85212500647
- ISSN
- 1864-564X
- DOI
- 10.1002/cssc.202402083
- language
- English
- LU publication?
- yes
- id
- 5270ca30-53e7-4ca2-84be-04a36817ffc6
- date added to LUP
- 2024-11-27 16:57:18
- date last changed
- 2025-06-03 14:26:49
@article{5270ca30-53e7-4ca2-84be-04a36817ffc6,
abstract = {{Advancing the use of air-sensitive polar organometallic Grignard and organolithium reagents under more environmentally benign conditions, here we report the addition of these reagents to a-b unsaturated ketones and aldehydes using the deep eutetic solvent (DES) choline chloride (ChCl): glycerol (Gly) (1:2), under air. Reactions occur at room temperature within seconds with excellent regioselective control. Furthering understanding of how these C-C bond forming processes take place in these reaction media, we have explored the surface concentration of the organic substrate (chalcone) in DES using interfacial tension and neutron reflectivity measurements, finding that chalcone is concentrated at the DES-hydrocarbon interface compared to the bulk concentration, although the interfacial chalcone concentration is still relatively low in this system. The influence of aggregation of the organometallic reagent in the organic solvent employed has also been evaluated, revealing the importance of achieving a balance between activation (via de-aggregation) and stability (to avoid its decomposition in the DES). This DES approach has been successfully extended to double additions to a-b unsaturated estes and for one pot sequential 1,4 and 1,2 additions to ketones, providing a new entry point to a range of tertiary-alcohols, minimising the use of organic solvents and avoiding intermediate time-consuming purification steps.}},
author = {{Platten, Andrew W. J. and Manasi, Iva and Campana, Mario and Edler, Karen J. and Hevia, Eva}},
issn = {{1864-564X}},
language = {{eng}},
month = {{04}},
publisher = {{John Wiley & Sons Inc.}},
series = {{ChemSusChem}},
title = {{Harnessing Deep Eutectic Solvents for Regioselective Polar Additions to <i>α</i>,<i>β</i> Unsaturated Ketones and Aldehydes}},
url = {{http://dx.doi.org/10.1002/cssc.202402083}},
doi = {{10.1002/cssc.202402083}},
year = {{2025}},
}