Elemental‐Sulfur‐Enabled Divergent Synthesis of Disulfides, Diselenides, and Polythiophenes from β‐CF₃‐1,3‐Enynes

Abstract

Divergent synthesis for precise constructions of cyclic unsymmetrical diaryl disulfides or diselenides and polythiophenes from CF3‐containing 1,3‐enynes and S8 was developed when the ortho group is F, Cl, Br, and NO2 on aromatic rings. Meanwhile, disulfides (diselenides) were also quickly constructed when the ortho group is H. These transformations undergo cascade thiophene construction/selective C3‐position thiolation process, featuring simple operations, divergent synthesis, broad substrate scope, readily available starting materials, and valuable products. A novel plausible radical annulation process was proposed and validated by DFT calculations for the first time. A series of derivatizations about the thiophene (TBT) and disulfides were also well‐represented.

A NaHCO3 Promoted Three‐component Cyclization: Easy Access to Benzodisulfide Heterocycles

“…In this newly developed three‐component reaction, elemental sulfur (S 8 ) is inexpensive and user‐friendly, [16,20] and 2‐halo‐phenylacetics are readily available [29,31] . Recently, Tang's group reported a decarboxylative multicomponent polymerization of p ‐phenylenediacetic acid, S 8 and aromatic diamines to convert S 8 into functional polythioamides with great structural diversity, large molecular weights and excellent yields [32] .…”

“…[4][5][6][7] Different sulfur sources, [8] e. g., potassium sulfide, [9] thiocyanate, [10] thiourea, [11] isothiocyanate, [12] thioamide, [13] thiophenol, [14] and elemental sulfur (S 8 ), [15] can be used to construct sulfur-containing heterocyclic compounds. Among them, due to the advantages of being nontoxic, odorless and chemically stable, S 8 has been widely used in the construction of organosulfur heterocycles through various strategies, [16][17][18] such as the direct addition to unsaturated bonds, [19] CÀ H bond functionalization, [20] and crosscoupling reactions of CÀ X (X = halide [21] or metal [22] ).…”

Insight into the Thiol-yne Kinetics via a Computational Approach

“…Click reactions have gained attention since they can occur with high yield under simple reaction conditions and allow the isolation of products easily. There are different types of addition reactions to alkynes, − and thiol-based reactions are one of the widely used in click chemistry − reactions since they can follow both nucleophile- and radical-based pathways. Over the last decades, the thiol-ene polymerization method has drawn attention, owing to its unique mechanism because the product of the reaction is in a regular step-growth network, despite the radical-mediated polymerization. ,, Another attractive thiol-based reaction is the thiol-yne reaction, which also pursues a radical- or nucleophile-based mechanism and can be considered as a sister reaction to the better-known thiol-ene mechanism.…”

Divergent oxidative dearomatization coupling reactions to construct polycyclic cyclohexadienones

“…3 Divergent synthesis allows the rapid acquisition of structurally diverse compounds from the same starting material and therefore has been a popular and useful tool in the discovery of bioactive molecules and functional materials. 4 Thus we intended to design a strategy for the divergent synthesis of different multifunctionalized cyclohexadienones from the same reactants.…”