Unusual Deoxidative Coupling Reaction of β-Sulfinyl Esters with Benzylic Trimethylammonium Salts

Abstract

A KOH-promoted unusual deoxidative coupling reaction of β-sulfinyl esters with benzylic trimethylammonium salts to produce thioethers is discovered for the first time. If quaternary ammonium salts synthesized from enantiomerically enriched amines are adopted, highly enantiomerically enriched benzyl thioethers (>95–99% ee) with configurations opposite to those of the enantiomerically enriched amines are obtained.

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

“…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. Besides, there has been no report on the exploration of the chemical space of oxidative transformation to generate sulfinate anions for sulfonylation.…”

Advances of Sulfenate Anions in Catalytic Asymmetric Synthesis of Sulfoxides

“…On the other hand, our research group have made a long-term research in organosulfur chemistry. [10][11][12][13][14][15][16][17] It is worth mentioning that we have recently disclosed an unprecedented transformation involving sulfenate anions, [16] which can be deoxygenation to give the reactive sulfide anion intermediates then coupling with benzylic trimethylammonium salts to produce highly enantioenriched chiral benzylic thioethers. In this review, we'll focus on the synthetic pathways toward chiral sulfoxides using sulfenate anions as key intermediates.…”

“…Based on these strategies toward sulfenate anions, various transformations have been developed by introduce nucleophiles to reacted with the sulfenate anion transient entities, in which, the most popular reactions are the routes led to sulfoxides, especially, enantioenriched sulfoxides. On the other hand, our research group have made a long‐term research in organosulfur chemistry [10–17] . It is worth mentioning that we have recently disclosed an unprecedented transformation involving sulfenate anions, [16] which can be deoxygenation to give the reactive sulfide anion intermediates then coupling with benzylic trimethylammonium salts to produce highly enantioenriched chiral benzylic thioethers.…”

One-Pot, Three-Component Assembly of Sulfides Using a Sulfoxide Reagent as a Sulfur Dication Equivalent

“…28 Recently, Zeng and co-workers have documented the synthesis of sulfides through deoxidative coupling of sulfenate anions with benzylic trimethylammonium salts. 29 A mechanism was postulated that involves thiolates as key reactive species to forge a C−S bond. The scope of reported sulfides is, however, inevitably narrow as one of the substituents in the products must be a benzyl derivative.…”

“…Organic synthesis involving sulfenate anions has made significant advances over the last decades, but product classes accessible via sulfenate anions have been mostly limited to sulfoxides . Recently, Zeng and co-workers have documented the synthesis of sulfides through deoxidative coupling of sulfenate anions with benzylic trimethylammonium salts . A mechanism was postulated that involves thiolates as key reactive species to forge a C–S bond.…”