Recent trends in the synthesis and applications of ß-iodovinyl sulfones: a decade of progress.

Direct vicinal difunctionalization of π-systems has emerged as a powerful platform for constructing multiple bonds in a single synthetic operation using simple chemical feedstocks. Over the past decade, there has been exponential growth in the direct construction of successive C-S and C-I bonds using a wide variety of sulfonyl and iodide reactants through 1,2-iodosulfonylation of alkynes in a regio- and stereo-selective manner. In this review, we mainly focus on the recent developments in the preparation of ß-iodovinyl sulfones and their practical applications in organic synthesis. The most promising photoredox and electrochemical transformations for synthesizing ß-iodovinyl sulfones are also reviewed. The multifunctional ß-iodovinyl sulfones have recently been burgeoning as versatile synthetic precursors due to the combination of vinyl iodide and vinyl sulfone moieties, essential building blocks for diverse synthetic manipulations. We hereby present the chemistry of ß-iodovinyl sulfones, which can be classified into numerous sections based on the sulfonyl surrogates, and potential synthetic approaches are systematically outlined.

Unified Radical Sulfonylative-Annulation of 1,6-Enynols with Sodium Sulfinates: A Modular Synthesis of 2,3-Disubstituted Benzoheteroles.

Benzoheteroles are valuable scaffolds in medicinal chemistry, but the direct synthesis of 3-vinyl benzoheterole analogues remains unexplored. A rationally designed new class of 1,6-enyne-containing propargylic alcohols has been prepared for the modular synthesis of 3-alkenyl benzoheteroles. Ag-catalyzed cascade radical sulfonylative-cycloannulation of 1,6-enynols with sodium sulfinates is realized to access a wide variety of 2,3-disubstituted benzoheteroles in good to high yields. Moreover, a three-component coupling of 1,6-enynols, aryldiazonium salts, and Na2S2O5 (as an SO2 surrogate) has been achieved to deliver benzoheterole derivatives in moderate to good yields. Of note, a scalable reaction and late-stage synthetic transformations were successfully demonstrated. A plausible mechanism is also presented based on the existing experimental results and control experiments.

Solvent-Driven Mono- and Bis-sulfenylation of (E)-ß-Iodovinyl Sulfones with Thiols for Flexible Synthesis of 1,2-Thiosulfonylalkenes and 1,2-Dithioalkenes.

The nature of solvent is a key factor for stereoselective mono- and bis-thiolation of (E)-ß-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-ß-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-ß-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, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-ß-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.

Synthesis and applications of sodium sulfinates (RSO2Na): a powerful building block for the synthesis of organosulfur compounds.

This review highlights the preparation of sodium sulfinates (RSO2Na) and their multifaceted synthetic applications. Substantial progress has been made over the last decade in the utilization of sodium sulfinates emerging as sulfonylating, sulfenylating or sulfinylating reagents, depending on reaction conditions. Sodium sulfinates act as versatile building blocks for preparing many valuable organosulfur compounds through S-S, N-S, and C-S bond-forming reactions. Remarkable advancement has been made in synthesizing thiosulfonates, sulfonamides, sulfides, and sulfones, including vinyl sulfones, allyl sulfones, and ß-keto sulfones. The significant achievement of developing sulfonyl radical-triggered ring-closing sulfonylation and multicomponent reactions is also thoroughly discussed. Of note, the most promising site-selective C-H sulfonylation, photoredox catalytic transformations and electrochemical synthesis of sodium sulfinates are also demonstrated. Holistically, this review provides a unique and comprehensive overview of sodium sulfinates, which summarizes 355 core references up to March 2020. The chemistry of sodium sulfinate salts is divided into several sections based on the classes of sulfur-containing compounds with some critical mechanistic insights that are also disclosed.