Recent Advances in Visible‐Light‐Driven C−S Bond Formation

Abstract

Due their multifaced applications, the access to organosulfur derivatives in an efficient and economical way is a challenge in organic synthesis. In this context photochemistry and photocatalysis play a crucial role in the development of innovative (and selective) Carbon‐Sulphur bond formation processes. The present review aims to collect the most recent strategies to achieve this target under visible light driven conditions.

Photocatalyst‐ and Transition‐Metal‐Free Light‐Induced Formation of Carbon‐Chalcogen Bonds

“…[51] A cost-effective and sustainable approach to forming CÀ S bonds is always recommended due to its versatility. [52] Traditionally, CÀ S bond formation was achieved through metalcatalyzed cross-coupling of thiols or disulfides with aryl halides, arylboronic acid, etc. [53] However, lightinduced strategies without photocatalysts and metals are in considerable demand as greener, more affordable alternatives to conventional approaches.…”

“…Carbon‐sulfur bonds were widely found in organic materials, natural products, and pharmaceutical and agricultural chemicals [51] . A cost‐effective and sustainable approach to forming C−S bonds is always recommended due to its versatility [52] . Traditionally, C−S bond formation was achieved through metal‐catalyzed cross‐coupling of thiols or disulfides with aryl halides, arylboronic acid, etc [53] .…”

Recent advances in selective mono-/dichalcogenation and exclusive dichalcogenation of C(sp2)–H and C(sp3)–H bonds

“…1). The carbon–chalcogen bond formation represents one of the most powerful methods for synthesizing organochalcogen compounds and it has been achieved mainly through cross-coupling, addition reactions and C–H chalcogenation, utilizing diverse chalcogen sources 14–19 under transition metal-catalyzed/mediated, 20–26 metal-free, 27–31 photocatalyzed, 32–36 electrochemical, 37 organocatalyzed 38,39 or enzymatic conditions. 40 As one of the most commonly employed protocols, transition-metal-catalyzed/mediated cross-couplings generally employ organic (pseudo)halides as reaction partners, 19,41–44 however, recent years have also witnessed the increasing use of other sources such as organic boronic acids, carboxylic acids, amines, phenols/alcohols, aldehydes, or esters as the coupling partners.…”

Photochemical halogen-bonding assisted carbothiophosphorylation reactions of alkenyl and 1,3-dienyl bromides

“…The development of novel synthetic methodologies for the construction of C–S bonds is an important undertaking in organic chemistry. 1 In particular, the design of new organic transformations oriented to the formation of sulfur-containing organophosphorous compounds is particularly attractive. This is due to the interesting properties these compounds feature from both a biological and chemical point of view.…”