New Design of a Disulfurating Reagent: Facile and Straightforward Pathway to Unsymmetrical Disulfanes by Copper‐Catalyzed Oxidative Cross‐Coupling

Abstract

A novel reagent, which introduces two sulfur atoms in one step, was designed and used for the construction of diverse disulfanes by copper-catalyzed oxidative cross-coupling under mild reaction conditions. By applying this stable and readily prepared reagent, late-stage modification of pharmaceuticals and natural products can be achieved straightforward. The scaled-up experiments further indicated the practicality of this protocol. The pH value of the system plays a key role in achieving highly selective cleavage of the C-S bond instead of a S-S bond in the transformation.

Thiosulfonates as Emerging Reactants: Synthesis and Applications

“…Strong electron‐withdrawing groups on the thiobenzoic acids 127 (e.g., nitro‐groups) led to longer reaction times and use of an amine both as activator of the thiol and as a trapping agent of the liberated sulfinic acid ( 19 ). Aliphatic thioacids ( 129 , 131 ) could also be used and in some case the salt was used [e.g., potassium thioacetate ( 131 )] . These reactants have been used for the construction of diverse unsymmetrical disulfides by oxidative cross‐coupling …”

“…Aliphatic thioacids ( 129 , 131 ) could also be used and in some case the salt was used [e.g., potassium thioacetate ( 131 )] . These reactants have been used for the construction of diverse unsymmetrical disulfides by oxidative cross‐coupling …”

Glycosyl disulfides: importance, synthesis and application to chemical and biological systems

“…The efficiency of this approach was generalised with regards to aryl boronic acids and different disulfurating reagents, including use of galactose as substrate, and constituted the first examples of metal-catalysed reactions to synthesise unsymmetrical glycosyl disulfides. 58 Furthermore, this copper-catalyzed cross coupling reaction could be tuned to different classes of products, and when a phenanthroline derivative was used as ligand and methanol as solvent, the same authors obtained the respective methoxy disulfide (SSOMe) instead. This umpolung strategy, in which the nucleophilic acetyl disulfide was converted into the electrophilic methoxy disulfide opened up a new avenue and enabled the reaction with a wide number of C-, N-, and S-nucleophiles to produce mixed glycosyl disulfides, aza-disulfides and trisulfides (Scheme 11C).…”

Steric and stereoscopic disulfide construction for cross-linkage via N-dithiophthalimides

“…To meet diverse requirements, masked disulfurating reagents (RSSAc and RSSOMe) were developed by us to incorporate RSS moieties into multifarious systems (Scheme 1c). 14,15 Considering the great importance of steric and stereoscopic disuldes, we are intrigued by disulfuration of a-branched esters to access diverse hindered disuldes. Nevertheless, steric hindrance of a-branched esters is the rst barrier for disulfuration.…”