This review provides a unique and comprehensive overview of sodium sulfinates for synthesizing many valuable sulfur-containing compounds, such as thiosulfonates, sulfonamides, sulfides, sulfones, allyl sulfones, vinyl sulfones and β-keto sulfones.

An unprecedented reactivity of (E)‐β‐iodovinyl sulfones in the presence of NaOAc is reported. The (E)‐β‐iodovinyl sulfones were treated with NaOAc in DMSO/H2O to yield β‐keto sulfones in moderate to high yields. A novel oxidative difunctionalization of β‐iodovinyl sulfones with thiosulfonates and NaOAc in DMF has been developed. This metal‐free oxosulfenylation is an operationally simple to access a wide range of β‐keto thiosulfones (α‐thioaryl‐β‐keto sulfones) in moderate to high yields. The transformations were reliable at gram‐scale, thus illustrating its efficiency and practicality. A plausible mechanism for the protocol is also proposed.

The nature of solvent is a key factor for stereoselective monoand bis-thiolation of (E)-β-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-βiodovinyl sulfones with thiols under the influence of K 2 CO 3 /DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-β-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)-and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K 2 CO 3 -mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-β-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.

A new and highly efficient vicinal thiosulfonylation of 1,1-dibromo-1-alkenes with thiosulfonates in the presence of cesium carbonate has been developed. The metal-free diheterofunctionalization is an operationally simple to access a wide range of (E)-1,2-thiosulfonylethenes (a-aryl-b-thioarylvinyl sulfones) in moderate to high yields with high levels of stereoselectivities. Further, scalable reactions have been demonstrated for this transformation, thus illustrating its efficiency and practicality.