Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides

• Malcolm J. D’Souza and
• Dennis N. Kevill

Beilstein J. Org. Chem. 2022, 18, 120–132, doi:10.3762/bjoc.18.13

• Transfer Reactions”. The present review will emphasize more recent contributions and, in particular, the application of the extended Grunwald–Winstein equation and kinetic solvent isotope effects to the solvolysis reactions. There is also an appreciable number of reports concerning the corresponding

• . The solvolyses of these additional types of sulfur(VI) substrates will be the topics of a future review. Keywords: correlation; Grunwald–Winstein equation; Hammett equation; mechanism; solvolysis; sulfonyl halides; Review 1. Introduction to solvolyses of sulfonyl halides In medicinal chemistry

• majority of solvolysis reactions, one also needs to evaluate the nucleophilic attack by the solvent which contributes modestly to the overall scheme for tert-butyl chloride solvolyses but appreciably for the solvolyses of methyl and primary alkyl halides. The original Grunwald–Winstein equation can be

Kinetic evaluation of the solvolysis of isobutyl chloro- and chlorothioformate esters

• Malcolm J. D’Souza,
• Matthew J. McAneny,
• Dennis N. Kevill,
• Jin Burm Kyong and
• Song Hee Choi

Beilstein J. Org. Chem. 2011, 7, 543–552, doi:10.3762/bjoc.7.62

• activation values obtained from Arrhenius plots for 1 in these five solvents are reported. The specific rates of solvolysis were analyzed using the extended Grunwald–Winstein equation. Results obtained from correlation analysis using this linear free energy relationship (LFER) reinforce our previous

• -1,1-dimethylethyl [9], n-propyl [10], isopropyl [11][12], n-octyl [13], and neopentyl [14] chloroformate esters, and those of methyl [15], ethyl [8], and isopropyl [16] chlorothioformate esters have been successfully analyzed using the extended [17][18][19] Grunwald–Winstein equation (Equation 1). In

• corresponding 3-D structures 1', 2', 3', 4' and 5' are shown in the most stable geometries for RXCXCl (where X = S or O) which exist in a conformation where the C=X is syn with respect to R. In a recent review [17], commemorating the 60th anniversary of the Grunwald–Winstein equation, we previously published