Recent advances in thiolation via sulfur electrophiles

Abstract

Umpolung of thiols has become a common strategy for the synthesis of various S-containing compounds and thus a series of sulfur electrophilies have been designed and applied for diverse thiolation....

Construction of alkynyl and acyl disulfides directly through thiol-modification withN-alkynylthio phthalimides under acid catalysis

“…Initially, the catalytic TFA promoted the release of the alkynylthio electrophile to form alkynyl disulfide 3 through S N 2 type S–S bond formation. 13,14 The product 3 could be isolated or further activated under TMSOTf catalysis. Due to the stabilization of sulfur to the vinyl carbocations, the formed intermediate A was captured by the oxygen of sulfoxides to generate the intermediate B .…”

Strategies and Methods for the Synthesis of 2‐Pyrazolines: Recent Developments (2012–2022)

“…Given the recent reports of N-(arylthio)succinimide as an efficient electrophilic arylthiol source [102] and the importance of arylthiol-substituted derivatives, [103] Wang and Li recently developed a method for the boron-mediated cyclization of β,γ-unsaturated hydrazones 307 with N-(arylthiol)succinimides 308 to yield pyrazolines 309 (Scheme 65). The authors screened various acids and additives, including MsOH, which has previously been used for similar oxythiolation reactions; however, BF 3 • OEt 2 in DCE was the acid that provided the highest yields.…”

Copper(i)-catalyzed multicomponent interrupted click reaction: modular synthesis of triazole sulfides from elemental sulfur

“…4 Recently, another electrophilic sulfuration method employing different nucleophiles has been developed. 5 Preparation in advance of the reactive electrophilic sulfuration reagents that are used is necessary, but the syntheses of these reagents usually require multiple steps, and more importantly, highly reactive reagents are difficult to prepare in large quantities and they easily decompose during storage, thus limiting their practical use.…”

“…5 a ,14 The use of benzenesulfonothioates as electrophiles is important because it can intercept the cuprate-triazole intermediate ( M 1 ) forming 5-thiotriazoles, and other less reactive electrophiles fail to do so. With our long-standing interest in the click reaction and sulfur chemistry, 5,14 we envisioned a new interrupted click reaction of active sulfur electrophiles formed in situ from the simplest precursors including elemental sulfur and aromatic or alkyl halides (Fig. 2c).…”