The alkaline hydrolysis of sulfonate esters : challenges in interpreting experimental and theoretical data
Duarte, Fernanda ; Geng, Ting ; Marloie, Gaël ; Al Hussain, Adel O ; Williams, Nicholas H and Kamerlin, Shina Caroline Lynn LU
(2014)
In The Journal of Organic Chemistry
79(7).
p.28-2816
- Abstract
Sulfonate ester hydrolysis has been the subject of recent debate, with experimental evidence interpreted in terms of both stepwise and concerted mechanisms. In particular, a recent study of the alkaline hydrolysis of a series of benzene arylsulfonates (Babtie et al., Org. Biomol. Chem. 10, 2012, 8095) presented a nonlinear Brønsted plot, which was explained in terms of a change from a stepwise mechanism involving a pentavalent intermediate for poorer leaving groups to a fully concerted mechanism for good leaving groups and supported by a theoretical study. In the present work, we have performed a detailed computational study of the hydrolysis of these compounds and find no computational evidence for a thermodynamically stable... (More)
Sulfonate ester hydrolysis has been the subject of recent debate, with experimental evidence interpreted in terms of both stepwise and concerted mechanisms. In particular, a recent study of the alkaline hydrolysis of a series of benzene arylsulfonates (Babtie et al., Org. Biomol. Chem. 10, 2012, 8095) presented a nonlinear Brønsted plot, which was explained in terms of a change from a stepwise mechanism involving a pentavalent intermediate for poorer leaving groups to a fully concerted mechanism for good leaving groups and supported by a theoretical study. In the present work, we have performed a detailed computational study of the hydrolysis of these compounds and find no computational evidence for a thermodynamically stable intermediate for any of these compounds. Additionally, we have extended the experimental data to include pyridine-3-yl benzene sulfonate and its N-oxide and N-methylpyridinium derivatives. Inclusion of these compounds converts the Brønsted plot to a moderately scattered but linear correlation and gives a very good Hammett correlation. These data suggest a concerted pathway for this reaction that proceeds via an early transition state with little bond cleavage to the leaving group, highlighting the care that needs to be taken with the interpretation of experimental and especially theoretical data.
(Less)
- author
- Duarte, Fernanda
; Geng, Ting
; Marloie, Gaël
; Al Hussain, Adel O
; Williams, Nicholas H
and Kamerlin, Shina Caroline Lynn
LU
- publishing date
- 2014-04-04
- type
- Contribution to journal
- publication status
- published
- keywords
- Alkaloids/chemistry, Benzenesulfonates/chemistry, Cyclic N-Oxides/chemistry, Esters, Hydrolysis, Kinetics, Mesylates/chemistry, Models, Theoretical, Molecular Structure, Pyridines/chemistry, Pyridinium Compounds/chemistry
- in
- The Journal of Organic Chemistry
- volume
- 79
- issue
- 7
- pages
- 13 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:24279349
- scopus:84893835841
- ISSN
- 1520-6904
- DOI
- 10.1021/jo402420t
- language
- English
- LU publication?
- no
- id
- d135cd55-d53f-472f-a9e6-a526e352c262
- date added to LUP
- 2025-01-11 21:58:47
- date last changed
- 2025-04-20 11:55:16
@article{d135cd55-d53f-472f-a9e6-a526e352c262,
abstract = {{<p>Sulfonate ester hydrolysis has been the subject of recent debate, with experimental evidence interpreted in terms of both stepwise and concerted mechanisms. In particular, a recent study of the alkaline hydrolysis of a series of benzene arylsulfonates (Babtie et al., Org. Biomol. Chem. 10, 2012, 8095) presented a nonlinear Brønsted plot, which was explained in terms of a change from a stepwise mechanism involving a pentavalent intermediate for poorer leaving groups to a fully concerted mechanism for good leaving groups and supported by a theoretical study. In the present work, we have performed a detailed computational study of the hydrolysis of these compounds and find no computational evidence for a thermodynamically stable intermediate for any of these compounds. Additionally, we have extended the experimental data to include pyridine-3-yl benzene sulfonate and its N-oxide and N-methylpyridinium derivatives. Inclusion of these compounds converts the Brønsted plot to a moderately scattered but linear correlation and gives a very good Hammett correlation. These data suggest a concerted pathway for this reaction that proceeds via an early transition state with little bond cleavage to the leaving group, highlighting the care that needs to be taken with the interpretation of experimental and especially theoretical data.</p>}},
author = {{Duarte, Fernanda and Geng, Ting and Marloie, Gaël and Al Hussain, Adel O and Williams, Nicholas H and Kamerlin, Shina Caroline Lynn}},
issn = {{1520-6904}},
keywords = {{Alkaloids/chemistry; Benzenesulfonates/chemistry; Cyclic N-Oxides/chemistry; Esters; Hydrolysis; Kinetics; Mesylates/chemistry; Models, Theoretical; Molecular Structure; Pyridines/chemistry; Pyridinium Compounds/chemistry}},
language = {{eng}},
month = {{04}},
number = {{7}},
pages = {{28--2816}},
publisher = {{The American Chemical Society (ACS)}},
series = {{The Journal of Organic Chemistry}},
title = {{The alkaline hydrolysis of sulfonate esters : challenges in interpreting experimental and theoretical data}},
url = {{http://dx.doi.org/10.1021/jo402420t}},
doi = {{10.1021/jo402420t}},
volume = {{79}},
year = {{2014}},
}