Palladium-Catalyzed Methylsulfonylation of Alkyl Halides Using Dimethyl Sulfite as SO₂ Surrogate and Methyl Source

Abstract

A novel and efficient method for the synthesis of methyl sulfone derivatives via palladium-catalyzed methylsulfonylation of alkyl halides with dimethyl sulfite has been described. A variety of aryl and alkyl iodides underwent the sulfonylation smoothly to furnish methyl sulfites in moderate to excellent yields.

Nickel‐Catalyzed Microwave‐Mediated Methylsulfonylation of Alkyl Halides

“…Recently, Xing et al. established a simple and direct method for methylsulfonylation of alkyl halides (Scheme 1b) [13] . However, longer reaction time (typically 18 h) was essential to accomplish average yield of methyl sulfones.…”

S-(Methyl-d3) Arylsulfonothioates: A Family of Robust, Shelf-Stable, and Easily Scalable Reagents for Direct Trideuteromethylthiolation

“…Then bromination and subsequent cyclization took place to give the final D-labeled rofecoxib 28 in acceptable yield. 16 Accordingly, D-labeled firocoxib could be prepared in only four steps from iodobenzene (for details, see the Supporting Information).…”

“…Treated by Oxone under aqueous conditions, trideuteromethylthioester could be converted into the corresponding trideuteromethylated sulfone which was not purified by silica gel chromatography. Then bromination and subsequent cyclization took place to give the final D-labeled rofecoxib 28 in acceptable yield . Accordingly, D-labeled firocoxib could be prepared in only four steps from iodobenzene (for details, see the Supporting Information).…”

TBAI-Mediated Cyclization and Methylsulfonylation of Propargylic Amides with Dimethyl Sulfite

“…Therefore, it is still highly desirable to develop an environmentally friendly strategy for the synthesis of methylsulfonylated compounds. Recently, sulfites have received significant attention as potent SO 2 surrogates, our group has also developed a ring-opening methylation of benzothiazoles by using dimethyl sulfite as a methylating reagent . On the basis of these reports, we envisioned whether methylsulfonyl compounds could be synthesized using dimethyl sulfite as both a SO 2 surrogate and methylating reagent.…”