Direct Trideuteromethylation of Sulfenate Anions Generated In Situ from ß-Sulfinyl Esters: An Access to Trideuteromethyl Sulfoxides.

Deuterated organic molecules have immense value in the pharmaceutical industry. Here, we present a synthetic strategy for direct trideuteromethylation of sulfenate ions derived in situ from ß-sulfinyl esters in the presence of a base utilizing inexpensive and abundant CD3OTs as the electrophilic trideuteromethylating agent. This protocol provides straightforward access to an array of trideuteromethyl sulfoxides in yields of 75-92% with a high degree of deuteration. The ensuing trideuteromethyl sulfoxide can be readily modified into trideuteromethyl sulfone and sulfoximine.

Heteroarylation of Sulfenate Ions In Situ Generated from ß-Sulfinyl Esters under Transition-Metal-Free Conditions.

Heteroaryl sulfoxides are an integral part of several bioactive molecules and pharmaceuticals. We have described a transition-metal-free route for the direct sulfinylation of 2-halobenzothiazoles and 2-halobenzimidazoles using ß-sulfinyl esters as the source of the sulfenate ion in the presence of a Brønsted base such as LiOtBu, and the corresponding heteroaryl sulfoxides were isolated in yields of 30 to 94%. Moreover, we hypothesized a plausible concerted nucleophilic aromatic substitution (cSNAr) pathway for the direct incorporation of sulfinyl functionality into the 2-haloheteroarenes.