Nucleophilic attack of 2-sulfinyl acrylates: A mild and general approach to sulfenic acid anions

Abstract

An increasing number of reactions of sulfenic acid anions are being demonstrated in the literature. As such, mild, general and reliable means for the generation of sulfenates are due. In the current paper, an addition/elimination of 2-sulfinyl acrylates using various nucleophiles is demonstrated and evaluated as a protocol for alkane- and arenesulfenate generation. Cyclohexanethiolate, methoxide and n-butyllithum each exhibit some merit for the reaction, and the thiolate is established as a mild, selective and effective reagent to release sulfenates from 2-sulfinyl acrylates. The stereospecificity of the addition/elimination of each nucleophile is recognized, and an explanation for the specificity is offered for thiolate and methoxide.

Conformers of Cysteine and Cysteine Sulfenic Acid and Mechanisms of the Reaction of Cysteine Sulfenic Acid with 5,5-Dimethyl-1,3-cyclohexanedione (Dimedone)

“…Owing in part to their high reactivity and instability, relatively little is known about their chemistry, properties, and structural parameters. However, sulfenic acids and their derivatives are useful reagents that play important roles as reactive intermediates in organosulfur chemistry and are implicated in a wide range of biochemical and chemical reactions. − Sulfenic acids have been trapped with 1,3-dicarbonyl compounds, alkenes, alkynes, and dienes. − Sulfenic acids are found in biological systems, are transient intermediates in certain protein functions in regulation, play vital roles in catalytic and signaling functions in proteins, − and are found in natural products including garlic and onion. − …”

Organocatalytic Asymmetric Synthesis of Sulfoxides from Sulfenic Acid Anions Mediated by a Cinchona-Derived Phase-Transfer Reagent

“…Quenching with alkyl halides to afford racemic compounds is well established. , Diastereoselective versions involving sulfenates possessing a stereogenic center or planar chirality have been described with a high degree of success . In contrast, enantioselective variants are limited to a single precedent from our group, in which the chiral influence of (−)-sparteine was evaluated and furnished a low 29% ee. , We anticipated that the use of a chiral phase-transfer catalyst 2 (PTC*) could be an alternative.…”

Unexpected reactions of Grignard reagents with selected β-carboalkoxy substituted sulfinate esters

“…The attack occurs in a conjugate fashion in relationship to the carboxylate and releases phenylsulfenate. 43,49 Ethyl 2-methoxycarbonylethanesulfinate (18) was prepared using protocols established for unsaturated sulfinate esters. 50 Its reaction with 3 equiv.…”