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Photo Lynn Kamerlin

Lynn Kamerlin

Professor

Photo Lynn Kamerlin

The alkaline hydrolysis of sulfonate esters : challenges in interpreting experimental and theoretical data

Author

  • Fernanda Duarte
  • Ting Geng
  • Gaël Marloie
  • Adel O Al Hussain
  • Nicholas H Williams
  • Shina Caroline Lynn Kamerlin

Summary, in English

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.

Publishing year

2014-04-04

Language

English

Pages

28-2816

Publication/Series

The Journal of Organic Chemistry

Volume

79

Issue

7

Document type

Journal article

Publisher

The American Chemical Society (ACS)

Keywords

  • Alkaloids/chemistry
  • Benzenesulfonates/chemistry
  • Cyclic N-Oxides/chemistry
  • Esters
  • Hydrolysis
  • Kinetics
  • Mesylates/chemistry
  • Models, Theoretical
  • Molecular Structure
  • Pyridines/chemistry
  • Pyridinium Compounds/chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 1520-6904