32 research outputs found

    Regioselective Synthesis of 2,4,5-Trisubstituted Oxazoles and Ketene Aminals via Hydroamidation and Iodo-Imidation of Ynamides

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    A novel and straightforward protocol is demonstrated for the synthesis of highly substituted oxazoles from readily accessible ynamides in the presence of ytterbium­(III) trifluoromethanesulfonate [Yb­(OTf)<sub>3</sub>], <i>N</i>-iodosuccinimide (NIS), and acetonitrile. Multiple oxazole skeletons in the aryl periphery are constructed in a single operation for the first time. The hydroamidation and iodo-imidation of ynamides to trisubstituted and tetrasubstituted ketene aminals is exemplified. An isotope labeling experiment is used to identify the oxygen source in this transformation. The reactions are scalable to the gram scale, testifying the robustness of the transformations

    Dimethyl Sulfoxide and <i>N</i>‑Iodosuccinimide Promoted 5-<i>exo-dig</i> Oxidative Cyclization of Yne-Tethered Ynamide: Access to Pyrrolidones and Spiro-pyrrolidones

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    An unprecedented metal-free dimethyl sulfoxide (DMSO) and <i>N</i>-iodosuccinimide mediated regioselective 5-<i>exo-dig</i> oxidative cyclization of an in situ generated enol equivalent of amides from ynamides bearing internal alkynes is demonstrated. The reaction allows easy access to functionalized pyrrolidone skeletons. Pyrrolidones having 3-<i>o</i>-biaryl motifs successfully undergo intramolecular electrophilic cyclization with the α,ÎČ-unsaturated olefin, furnishing spiro-pyrrolidone motifs. A one-pot sequential 5-<i>exo-dig</i> cyclization of the yne-tethered ynamides, followed by electrophilic cyclization of the pyrrolidone, is presented. The role of DMSO in the transformation is clarified, and a tentative reaction pathway is proposed
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