Advances of Sulfenate Anions in Catalytic Asymmetric Synthesis of Sulfoxides

Abstract

In recent years, sulfenate anions as key intermediates in enantioselective synthesis have attracted considerable attention. Typically, development of novel synthetic methods to generate sulfenate anions allows for the preparation of various enantiopure sulfoxides, which are prevalently used as auxiliaries, ligands, organocatalysts, and biologically active compounds. This review presents the in situ preparation methods and the recent applications of sulfenate anions in catalytic asymmetric synthesis of chiral sulfoxides.

Dioxirane‐Based Stereoselective and Oxidative Transformations

“…Sulfoxides have myriads of applications in asymmetric synthesis, [67,68] drugs and biological studies [68–70] . Although the asymmetric oxidations of sulfides to sulfoxides are carried out using various methods, [70–77] the employment of dioxiranes for such oxidation offers transition metal‐free green [78,79] synthetic protocol. It is worth mentioning that the treatment of a highly functionalized chiral sulfide with a strong oxidant can result in unwanted side reactions leading to unexpected products with a low yield of the desired sulfoxide.…”

Redox transformation of β-sulfinyl esters for asymmetric synthesis of sulfone-based axially chiral styrenes

“…11 In contrast, the sulfenate anion is one of the most important intermediates for the synthesis and bioorganic transformations of sulfur-containing molecules. 12 Various precursors have been employed to generate sulfenate anions under trigger conditions in asymmetric sulfinylation, 13 and recently in unprecedented thiolation by deoxidative coupling with chiral benzylic trimethylammonium salts (Scheme 1a). 14 However, harsh conditions such as strong bases and high temperature (100 °C) are always required for the trigger.…”

Expanding the Use of Peroxygenase from Oat Flour in Organic Synthesis: Enantioselective Oxidation of Sulfides

“…The synthesis of chiral sulfoxides mainly relies on catalytic asymmetric oxidation of prochiral sulfides with benign oxidants, as tert -butyl hydroperoxide (TBHP) or H 2 O 2 , in the presence of metal-chiral ligand complexes or organocatalysts and an impressive variety of effective systems has been developed. This reaction is still considered the most general and convenient approach to the synthesis of optically active sulfoxides, although alternative strategies based on the enantioselective formation of C-S bond or kinetic resolution of racemic sulfoxides, have been also explored [ 19 , 20 , 21 , 22 ].…”