A gold-catalyzed 1,2-oxyalkynylation of N-allenamides with ethylnylbenziodoxolones (EBXs) has been achieved for the first time. The reaction, which follows a redox-neutral Au(I)/Au(III) catalytic pathway, was enabled in an attempt to exhaust the EBX reagents atom-economically by putting the nucleophilic carboxylate part of EBXs to appropriate use. This constitutes the first example for gold-catalyzed β-alkynylation of N-allenamides to construct highly valuable 1,3-enynes. The potential of the sequence is further documented by some follow-up transformations.

By applying the “interplay” mode, which consolidates two key reactivity modes of gold catalysis, namely π-activation mode and cross-coupling mode, the first alkynylative Meyer–Schuster rearrangement is designed and successfully implemented. The current protocol gives straightforward access to enynones, a highly valuable building block, from easily available propargyl alcohol feedstocks. Control experiments suggest an Au­(III) catalyst triggers the Meyer–Schuster rearrangement, whereas monitoring the reaction with ESI-HRMS provided strong evidence in favor of a key alkynylgold­(III) intermediate which supports the proposed “interplay” scenario.

Immunogenic Cell Death (ICD) is a unique cell death mechanism that kills cancer cells while rejuvenating the anticancer immunosurveillance, thereby benefiting the clinical outcomes of various immuno-chemotherapeutic regimens. Herein, we...

It takes two to tango: an experimental and computational study of ionic liquid crystals reveals the subtle balance between the energetic interactions in the hydrophobic and ionic layers that contribute to the stabilization of the ionic smectic phase.