Recent Advances in the Direct Synthesis of Sulfur‐Containing Organophosphorus Compounds via Radical Processes

Abstract

Phosphonothioates, phosphinothioates and phosphorothioates are regarded as an important class of sulfur‐containing organophosphorus compounds. Because of the unique P(O)S−R group, these compounds have important biological activities and thus have been widely used in the fields of pharmaceuticals and pesticides. In recent years, the development of sulfur‐containing organophosphorus compounds by radical processes has attracted considerable attention in organophosphorus chemistry. Along these lines, in this review, the recent advances in the synthesis of sulfur‐containing organophosphorus compounds were systematically summarized. According to the different ways of generating radicals during the formation process of phosphonothioates, phosphinothioates and phosphorothioates, these transformations can be divided into four categories: (1) Oxidant or metal‐free promoted radical transformation to fabricate sulfur‐containing organophosphorus compounds; (2) Copper‐catalyzed radical transformation to produce sulfur‐containing organophosphorus compounds; (3) Photo‐induced radical transformation to prepare sulfur‐containing organophosphorus compounds; (4) Electro‐induced radical transformation to derive sulfur‐containing organophosphorus compounds.

Three-component coupling reaction of white phosphorus, alcohols and diaryl disulfides: a chlorine-free avenue for accessing phosphorothioates

“…9,10 Numerous efforts have been made to study P–S–C bond formation, leading to the development of various strategies over the past few decades. 11 The most commonly used method is the Michaelis–Arbuzov reaction, which involves nucleophilic substitution of sulfenyl halides ArSX or other sulfur-based reagents with phosphites (Scheme 1a). 12,13 The Atherton–Todd-type reaction, typically performed using toxic tetrachloromethane as a halogenating reagent and solvent, provides an alternative route for these scaffolds (Scheme 1b).…”

Chemodivergent phosphonylation of diazocarboxylates: light-on vs. light-off reactions

“…4 Therefore, numerous synthetic methods to incorporate phosphorus into organic scaffolds have been invented. 5 Yet development of more efficient protocols to access various organophosphorus molecules is highly desired.…”

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

“…6 The significance of these compounds is underscored by the numerous methodologies that have been documented in recent years centered around their synthesis. 7 While both metal-catalyzed 8 and metal-free 9 procedures have been well established for creating S -arylated phosphorothioates (Scheme 1b), we could only find one example of a synthetic methodology for the preparation of the analogous S -alkenylated compounds. 10 However, this protocol contemplates a very limited scope (6 examples), making use of uncommon iodonium salts.…”