Visible-light-driven multicomponent reactions to access S-alkyl phosphorothioates using elemental sulfur as the sulfur source

Abstract

A convenient and eco-friendly visible-light promoted multicomponent protocol has been developed for the synthesis of S-alkyl phosphorothioates by using elemental sulfur as the cheap and odorless sulfur source.

Visible-Light-Initiated Multicomponent Reactions of α-Diazoesters to Access Organophosphorus Compounds

“…On the basis of the above experiments and referring to previous reports, − a possible reaction mechanism was proposed as shown in Scheme . First, the photoexcitation of methyl phenyldiazoacetate 1a formed an excited state 1a* , which underwent denitrogenation to give free carbene intermediate 6a under visible-light irradiation.…”

“…Since Szabó and Koenigs independently reported metal-catalyzed and photochemical ring opening of cyclic ethers with diazo compounds and N -fluorobenzenesulfonimide, multicomponent reactions of aryldiazoacetates, cyclic ethers, and nucleophiles have attracted great attention of chemists in synthetic community . Very recently, our group also described visible-light-promoted strategy for the preparation of S -alkyl phosphorothioates through base-mediated four-component reactions of α-diazoesters, elemental sulfur, cyclic ethers, and H-phosphonates . As our ongoing interest in the development of photochemical reactions, herein, we wish to present a new and efficient visible-light-promoted multicomponent reaction of α-diazoesters, cyclic ethers, and P­(O)H compounds to access a series of phosphonates and phosphinates under air (Scheme e).…”

“…20 Very recently, our group also described visiblelight-promoted strategy for the preparation of S-alkyl phosphorothioates through base-mediated four-component reactions of α-diazoesters, elemental sulfur, cyclic ethers, and H-phosphonates. 21 As our ongoing interest in the development of photochemical reactions, 22 herein, we wish to present a new and efficient visible-light-promoted multicomponent reaction of α-diazoesters, cyclic ethers, and P(O)H compounds to access a series of phosphonates and phosphinates under air (Scheme 1e).…”

Visible light-mediated photolysis of organic molecules: the case study of diazo compounds

“…74 Several multicomponent reactions involving the use of cyclic ethers as solvent and a variety of nucleophiles have been reported to afford the corresponding more complex formal O-H insertion products, which are also presumably derived from the involvement of a key oxygen ylide intermediate. 61,62,64,[75][76][77][78][79][80][81][82][83][84] C-C insertion reactions could be achieved with 1,3-diketones 85,86 (with a rare successful example of enantioselective catalysis being demonstrated by Hui and co-authors employing a chiral phosphoric acid catalyst 86 ), and enaminones. 87 Condensation-type products have been also obtained starting from azides to afford imines, 34 and starting from isonitriles to afford ketenimine derivatives.…”

C-3 Functionalization of 2-Aryl-2H-indazoles under Photo/Electrocatalysis

“…Photocatalytic synthesis uses renewable visible light to initiate the radical reaction to replace high-temperature heating. [20][21][22][23][24][25] Electrocatalysis is another common and environmentally friendly platform for redox-mediated transformation in organic synthesis. [26][27][28][29] It has the advantages of convenience, environmental sustainability, and controllability by changing potential, current or total charge.…”