# The Synthesis and Characterization of Selected Optically Active Sulfoxides Bearing Perfluorocumyl Moiety, Their Spontaneous Reversible Transformations into Higher-Valent Organosulfur Species–Bicyclic Hydroxysulfuranes, and Their Irreversible Transformation into Sultine

## TL;DR

This paper describes the synthesis and transformation behavior of new optically active sulfoxides containing perfluorocumyl groups.

## Contribution

The study reports the synthesis of novel sulfoxides and their spontaneous transformations into higher-valent sulfur species and irreversible conversion into sultine.

## Key findings

- The synthesized sulfoxides exhibit equilibrium between sulfoxide and hypervalent sulfurane forms in solution.
- Compound 3 irreversibly transforms into a cyclic sulfinate ester (sultine) in solution.
- The transformation mechanism was confirmed using GC-MS and analog compound analysis.

## Abstract

The preparation of the novel optically active sulfoxides (-)-(S)-1,1,1,3,3,3-hexafluoro-2-[o-(p-tolylsulfinyl)phenyl]propan-2-ol 1, (-)-(S)-1,1,1,3,3,3-hexafluoro-2-[o-(methylsulfinyl)phenyl]propan-2-ol 2 and (-)-(S)-1,1,1,3,3,3-hexafluoro-2-[o-(t-butyl-sulfinyl)phenyl]propan-2-ol 3 according to the Andersen methodology and their spectroscopic characterization is presented. The NMR and CD spectroscopic evidence of the existence of the equilibrium between sulfoxide and hypervalent sulfurane forms of these compounds in solution and attempts at the isolation of corresponding sulfuranes are shown. For compound 3, the unprecedented subsequent irreversible transformation in solution into corresponding cyclic sulfinate ester–sultine 17 was established on the basis of NMR spectroscopy measurements. The mechanism of this transformation was investigated by means of GC-MS analysis and confirmed on the basis of synthesized long alkyl chain analog 23 transformation in solution. Moreover, the oxidation properties of obtained sulfoxides 2 and 3 for the selected compounds are described.