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.

Copper(I)‐Catalyzed Asymmetric Interrupted Kinugasa Reaction: Synthesis of α‐Thiofunctional Chiral β‐Lactams

“…Because of their unique structure and biological properties, molecules of this type have been widely used in food chemistry, chemical biology and in the pharmaceutical industry. [15] Symmetrical disulfides can be obtained by oxidative coupling of thiols, but synthesis of asymmetric disulfides [16] is still challenging and synthesis of asymmetric disulfides containing b-lactams has not been achieved to date. Here we report the first synthesis of chiral b-lactam disulfides by a disulfur transfer in an interrupted Kinugasa reaction (Table 4).…”

Substrate-controlled divergent synthesis withortho-vinyl-functionalised 1,3-enynes and iminesviapalladium catalysis

“…1 Over the past decades, a number of DOS strategies, such as the build/couple/pair approach, 2 two-directional synthesis, 3 etc., 4 have been developed for yielding collections of structurally distinct and complex molecules, which not only broadened chemical space but also served as potential chemical probes or drug leads. 5 Compared with fruitful divergent synthesis accomplished by tuning the catalysts, 6 ligands 7 or other parameters, 8 switchable elaboration of similar starting materials into divergent but distinct products, especially skeletally diverse frameworks, under the identical catalytic conditions, has been less investigated and still represents a great challenge in organic synthesis. 9 1,3-Enynes have proven to be a class of versatile building blocks for the synthesis of multi-substituted alkenes, allenes and other compounds through metal-or organocatalystmediated 1,2-or 1,4-addition pathways.…”