Next Article in Journal
Indole Alkaloids from Catharanthus roseus: Bioproduction and Their Effect on Human Health
Previous Article in Journal
Inhibitory Effects of Neochamaejasmin B on P-Glycoprotein in MDCK-hMDR1 Cells and Molecular Docking of NCB Binding in P-Glycoprotein
Previous Article in Special Issue
Comparison of the Separation Performances of Cinchona Alkaloid-Based Zwitterionic Stationary Phases in the Enantioseparation of β2- and β3-Amino Acids
Article Menu

Export Article

Open AccessArticle
Molecules 2015, 20(2), 2949-2972; doi:10.3390/molecules20022949

Acid Catalyzed Alcoholysis of Sulfinamides: Unusual Stereochemistry, Kinetics and a Question of Mechanism Involving Sulfurane Intermediates and Their Pseudorotation

Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
*
Author to whom correspondence should be addressed.
Academic Editor: Derek J. McPhee
Received: 19 December 2014 / Accepted: 3 February 2015 / Published: 11 February 2015
(This article belongs to the Special Issue Dynamic Stereochemistry)
View Full-Text   |   Download PDF [1169 KB, uploaded 12 February 2015]   |  

Abstract

The synthesis of optically active sulfinic acid esters has been accomplished by the acid catalyzed alcoholysis of optically active sulfinamides. Sulfinates are formed in this reaction with a full or predominant inversion of configuration at chiral sulfur or with predominant retention of configuration. The steric course of the reaction depends mainly on the size of the dialkylamido group in the sulfinamides and of the alcohols used as nucleophilic reagents. It has been found that bulky reaction components preferentially form sulfinates with retention of configuration. It has been demonstrated that the stereochemical outcome of the reaction can be changed from inversion to retention and vice versa by adding inorganic salts to the acidic reaction medium. The unusual stereochemistry of this typical bimolecular nucleophilic substitution reaction, as confirmed by kinetic measurements, has been rationalized in terms of the addition-elimination mechanism, A-E, involving sulfuranes as intermediates which undergo pseudorotations. View Full-Text
Keywords: sulfur chirality; stereoselective synthesis; chiral sulfinamides; chiral sulfinates; enantiomer interconversion; nucleophilic substitution; addition-elimination mechanism; sulfuranes; pseudorotation sulfur chirality; stereoselective synthesis; chiral sulfinamides; chiral sulfinates; enantiomer interconversion; nucleophilic substitution; addition-elimination mechanism; sulfuranes; pseudorotation
Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Bujnicki, B.; Drabowicz, J.; Mikołajczyk, M. Acid Catalyzed Alcoholysis of Sulfinamides: Unusual Stereochemistry, Kinetics and a Question of Mechanism Involving Sulfurane Intermediates and Their Pseudorotation. Molecules 2015, 20, 2949-2972.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]

Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top