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Article

Nucleophilic Substitution at Tricoordinate Sulfur—Alkaline Hydrolysis of Optically Active Dialkoxysulfonium Salts: Stereochemistry, Mechanism and Reaction Energetics

by
Marian Mikołajczyk
1,*,
Bogdan Bujnicki
1,
Józef Drabowicz
1 and
Marek Cypryk
2,*
1
Department of Organic Chemistry, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, 90-363 Łódź, Poland
2
Department of Structural Chemistry, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, 90-363 Łódź, Poland
*
Authors to whom correspondence should be addressed.
Molecules 2022, 27(23), 8212; https://doi.org/10.3390/molecules27238212
Submission received: 7 October 2022 / Revised: 31 October 2022 / Accepted: 14 November 2022 / Published: 25 November 2022
(This article belongs to the Special Issue Theoretical Investigations of Reaction Mechanisms II)
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Abstract

Optically active dialkoxyisopropylsulfonium salts were obtained by methylation (ethylation) of optically active alkyl isopropanesulfinates using methyl (ethyl) trifluoromethanesulfonate. Alkaline hydrolysis of a series of methoxy(alkoxy)sulfonium salts afforded the two sulfinate products methyl isopropanesulfinate and alkyl isopropanesulfinate, both formed with a slightly prevailing inversion of configuration at the sulfur atom. DFT calculations revealed that this substitution reaction proceeded stepwise according to an addition-elimination (A–E) mechanism involving the formation of high tetracoordinate SIV sulfurane intermediates. In addition, the DFT calculations showed that recombination of the hydroxy anion with the methoxy(alkoxy)sulfonium cation—leading to the parallel formation of the two most stable primary sulfuranes, with the hydroxy and alkoxy groups in apical positions and their direct decomposition—is the most energetically favorable pathway.
Keywords: dialkoxysulfonium salts; alkaline hydrolysis; stereochemistry; addition-elimination (A–E) mechanism; pseudorotation; DFT calculations dialkoxysulfonium salts; alkaline hydrolysis; stereochemistry; addition-elimination (A–E) mechanism; pseudorotation; DFT calculations

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MDPI and ACS Style

Mikołajczyk, M.; Bujnicki, B.; Drabowicz, J.; Cypryk, M. Nucleophilic Substitution at Tricoordinate Sulfur—Alkaline Hydrolysis of Optically Active Dialkoxysulfonium Salts: Stereochemistry, Mechanism and Reaction Energetics. Molecules 2022, 27, 8212. https://doi.org/10.3390/molecules27238212

AMA Style

Mikołajczyk M, Bujnicki B, Drabowicz J, Cypryk M. Nucleophilic Substitution at Tricoordinate Sulfur—Alkaline Hydrolysis of Optically Active Dialkoxysulfonium Salts: Stereochemistry, Mechanism and Reaction Energetics. Molecules. 2022; 27(23):8212. https://doi.org/10.3390/molecules27238212

Chicago/Turabian Style

Mikołajczyk, Marian, Bogdan Bujnicki, Józef Drabowicz, and Marek Cypryk. 2022. "Nucleophilic Substitution at Tricoordinate Sulfur—Alkaline Hydrolysis of Optically Active Dialkoxysulfonium Salts: Stereochemistry, Mechanism and Reaction Energetics" Molecules 27, no. 23: 8212. https://doi.org/10.3390/molecules27238212

APA Style

Mikołajczyk, M., Bujnicki, B., Drabowicz, J., & Cypryk, M. (2022). Nucleophilic Substitution at Tricoordinate Sulfur—Alkaline Hydrolysis of Optically Active Dialkoxysulfonium Salts: Stereochemistry, Mechanism and Reaction Energetics. Molecules, 27(23), 8212. https://doi.org/10.3390/molecules27238212

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