Formate-Mediated Synthesis ofβ-Hydroxysulfides from Olefins and Thiosulfonates via EDA Complex Strategy under Visible Light Irradiation in Air

A visible-light-induced and efficient one-pot synthesis ofβ-hydroxysulfides from olefins,thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed.A plausible radical involved mechanism is proposed.During the reaction process,formates play a crucial role:first,as donors in the EDA complex;second,as providers of the hydrogen source;and third,by generating CO_(2)^(•–)to reduce peroxide intermediates,leading to the formation ofβ-hydroxysulfides.In contrast to the previously reported thiol-oxygen co-oxidation reactions,this simple and sustainable approach features mild reaction conditions,operational simplicity,odorless and excellent functional group tolerance.

1,n-Thiosulfonylation using thiosulfonates as dual functional reagents

In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the diverse synthesis of important S-containing derivatives.These 1,n-thiosulfonylation reactions usually feature simple procedures,100%atom economy,and high regioselectivity.This review focuses on the recent advancements in the transformations of thiosulfonates through 1,n-thiosulfonylation involving the formation of two distinct C-S bonds under transition-metal-catalyzed or metal-free conditions,where thiosulfonates act as both a sulfonyl and a sulfenyl component.

NBS-Promoted Sulfenylation of Sulfinates with Disulfides Leading to Unsymmetrical or Symmetrical Thiosulfonates

A highly practical method to access unsymmetrical and symmetrical thiosulfonates in moderate to excellent yields has been developed through NBS-promoted sulfenylation of sulfinates with disulfides. The present process enables the use of two RS in RSSR and shows broad functional group tolerance, which represents an atom-economical and practical procedure for the synthesis of thiosulfonates. A plausible mechanism for the role of NBS as a promoter for the cleavage of disulfides generating N-（organothio）succinimide that then undergos facile sulenylation with sulfinates is proposed.

TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols:Construction of thiosulfonate under transition-metal free conditions

A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported.The thiosulfonates were isolated in good yields with broad tolerance of functional group.Readily available inorganic Na2S2O5 was applied as the sulfur dioxide surrogate.This strategy features easily available substrates,mild reaction conditions and free transition-metal catalyst.