Metal-free C–S coupling of thiols and disulfides

Abstract

In organic synthesis, transition metal and photoredox catalysis based reaction systems are the emerging trends for construction of C-S bonds. Many review articles have timely appeared in this field, however,...

A photoexcited halogen-bonded EDA complex of the thiophenolate anion with iodobenzene for C(sp3)–H activation and thiolation

“… 9 Among those established synthetic protocols, the methods for formation of C–S bonds via functionalization of the C–H bond mainly focused on the C(sp 2 )–H bonds. 10 The thiolation of C(sp 3 )–H bonds normally relied on the cross-coupling of oxidatively generated radicals with disulfides 11 or in situ generated disulfides. 12 The disulfides were also applied to the nickel-catalyzed thiolation of β-methyl C(sp 3 )–H bonds of aliphatic carboxamides.…”

Transition Metal‐Free Sulfenylation of C−H Bonds for C−S Bond Formation in Recent Years: Mechanistic Approach and Promising Future

“…The transition metal-free sulfenylation of CÀ H bonds for CÀ S bond formation with aryl or alkyl group with sulfenylating agents is among the most studied class of CÀ S bond forming reactions in organic synthesis. [92] Over the decades, there is remarkable progress in the CÀ H activation using various catalysts such as base, graphene oxide, photo-induced, halide anion, iodine and inorganic or organic mild oxidizing agents. The present review is divided into two parts i. e., sulfenylation reactions proceeding via radical pathway and sulfenylation reactions proceeding via ionic pathway.…”

“…[167] Fan and co-workers [168] have reported a controlled catalytic approach for the synthesis of α-alkylthio β-ketosulfones (169) and α,β-disulfonyl ketones (170) using acetic acid and hydrochloric acid, respectively. The reaction between βketosulfones (168) and sulfoxides (92) in presence of acetic acid (1.5 mL) at 120 °C resulted into α-alkylthio-β-ketosulfones (169) in good to excellent yields. However, moderate yield of α,β-disulfonyl ketones (170) was observed when the catalyst was replaced by HCl (1 equiv.)…”

t BuOLi-promoted terminal alkyne functionalizations by aliphatic thiols and alcohols

“…21 Indeed, radical addition to terminal alkynes always gives either monofunctionalized products with Markovnikov selectivity or anti-Markovnikov selective products with mixtures of ( E )- and ( Z )-isomers. 10,22 In addition, it also provides various types of geminal or vicinal coupling products (Fig. 1a).…”