Straightforward Access to Thiocyanates via Dealkylative Cyanation of Sulfoxides

Abstract

Thiocyanates, versatile building blocks in organic synthesis, are shown to be easily accessible via an interrupted Pummerer reaction of sulfoxides. This facile dealkylative functionalization proceeds under mild conditions through electrophilic activation of the sulfoxide partner. The resulting thiocyanate itself can serve as a handle for diversification in a straightforward one-pot procedure.

Transition Metal-Free C–H Thiolation via Sulfonium Salts Using β-Sulfinylesters as the Sulfur Source

“…Recently, sulfonium salts have emerged as powerful intermediates for the site-selective late-stage C–H functionalization of arenes, in which sulfides such as tetrahydrothiophene, thianthrene, and dibenzothiophene were formed quantitatively as byproducts (Scheme a) . In addition, the selective cleavage of one of the three C–S bonds of aryl sulfonium salts via nucleophilic substitution was also realized to give aryl sulfides (Scheme b) . While this strategy is promising, alkenyl, alkynyl, and alkyl sulfonium salts were not tolerated due to the fact that both alkenyl and alkynyl sulfonium salts are good electrophilic Michael acceptors .…”

Transition-metal-free C–S bond cleavage and transformation of organosulfur compounds

“…Next, the addition of TMSCN to 15C was followed by a dealkylation process to provide the final thiocyanate 105 (Scheme 19c). 45…”

N1‐Methylthiomethylation of (8‐Aza)6‐Chloropurine with DMSO through the Pummerer Rearrangement

“…The sulfoxide product 8 a was obtained through the oxidation with m-CPBA and increasing the loading amount of m-CPBA further afforded the sulfone product 9 a. Furthermore, the sulfoxide in product 8 a was activated with trifluoromethanesulfonic anhydride under the conditions described in the literature, [59] and the resulting product 10 a, in ChemistrySelect which the methyl sulfoxide group was substituted with a methoxy group, was obtained in an isolated yield of 23 %.…”