The stereochemistry of substitution at S(VI)
File(s)
Published version
Author(s)
Symes, Oliver
Bull, James
Type
Journal Article
Abstract
Since the re-birth of sulfur-fluoride exchange (SuFEx) chemistry, coined by Sharpless in 2014 as a ‘click’ reaction, the prevalence of sulfur(VI) moieties in medicinal, polymer and materials chemistry has increased significantly. SuFEx and analogous substitution reactions at electrophilic S(VI) reagents are often performed on symmetrical, achiral S(VI) centres. However, when these substitution reactions are applied to chiral S(VI) substrates, often enantioenriched chiral-at-sulfur aza-S(VI) analogues, the stereochemical outcome of the reaction must be considered to obtain the appropriate 3D configuration. In this review, we aim to draw together the stereochemical outcomes and mechanistic understanding of substitution reactions occurring at electrophilic chiral S(VI) reagents to provide support, and potential word of caution, to the growing field. In addition, we review the significant developments in stereocontrolled reactions at S(VI) centres.
Date Issued
2025-12-07
Date Acceptance
2025-08-19
Citation
Organic Chemistry Frontiers, 2025, 12 (23), pp.6681-6697
ISSN
2052-4129
Publisher
Royal Society of Chemistry
Start Page
6681
End Page
6697
Journal / Book Title
Organic Chemistry Frontiers
Volume
12
Issue
23
Copyright Statement
Copyright © the Partner Organisations 2025. Open Access Article: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Publication Status
Published
Date Publish Online
2025-08-20