Organosulfur compounds have long
played a vital role in organic
chemistry and in the development of novel chemical structures and
architectures. Prominent among these organosulfur compounds are those
involving a sulfur(IV) center, which have been the subject of countless
investigations over more than a hundred years. In addition to a long
list of textbook sulfur-based reactions, there has been a sustained
interest in the chemistry of organosulfur(IV) compounds in recent
years. Of particular interest within organosulfur chemistry is the
ease with which the synthetic chemist can effect a wide range of transformations
through either bond formation or bond cleavage at sulfur. This review
aims to cover the developments of the past decade in the chemistry
of organic sulfur(IV) molecules and provide insight into both the
wide range of reactions which critically rely on this versatile element
and the diverse scaffolds that can thereby be synthesized.
The chemistry of the carbonyl group is essential to modern organic synthesis. The preparation of substituted, enantioenriched 1,3- or 1,5-dicarbonyls is well developed, as their disconnection naturally follows from the intrinsic polarity of the carbonyl group. By contrast, a general enantioselective access to quaternary stereocenters in acyclic 1,4-dicarbonyl systems remains an unresolved problem, despite the tremendous importance of 2,3-substituted 1,4-dicarbonyl motifs in natural products and drug scaffolds. Here we present a broad enantioselective and stereodivergent strategy to access acyclic, polysubstituted 1,4-dicarbonyls via acid-catalyzed [3,3]-sulfonium rearrangement starting from vinyl sulfoxides and ynamides. The stereochemistry at sulfur governs the absolute sense of chiral induction, whereas the double bond geometry dictates the relative configuration of the final products.
A mechanistic investigation of the acid-catalysed redox-neutral arylation of ynamides intertwining ESI-MS, DFT and experiments reveals diverse pathways available from an otherwise simple-looking transformation.
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