| The interest regarding sulfenate anions and their chemistry has been growing over recent years. Sulfenates have been pursued by a number of groups and are important as reactive intermediates in both organic and biochemical reactions. The Schwan group has demonstrated the first general protocol for the generation alkanesulfenate anions. This has been achieved through an efficient synthesis of a sulfinyl acrylate moiety that is a precursor to the sulfenate anion. The synthesis of the sulfenate precursor was optimized on a large scale. With this methodology, S-alkylation of protected cysteinesulfenate has been optimized using various alkyl halides, with yields ranging from 45-69% and drs as high as 21.2:1. The crude product afforded an interesting result; the sulfoxide may not be the immediate alkylation product. The O alkylated sulfenate ester was synthesized through traditional chemistry and shown to not be involved in the intermediate. A Li complex of the purified cysteinesulfoxide was created; it was found to be the cause of the odd 1H NMR shifts seen in the crude mixture. |
