The first reverse regioselective intermolecular annulation of aryl substituted 2-acetylenic ketones with O-substituted N-hydroxybenzamides or acrylamides followed by tandem cyclization via ruthenium-catalyzed C–H activation, is reported.

Fmoc-Leu-ψ[CH2NCS] undergoes a reversible isomorphous phase transition upon cooling. The crystal structure at 100 K displays a short N=C=S···N=C=S intermolecular interaction, which has been characterized based on experimental charge density analysis, as a stabilizing interaction with both σ-holes and π-holes acting cooperatively.

A novel class of optically active N-Fmoc-protected amino isonitriles has been described for the first time. Conversion of the carboxyl group of Fmoc-beta-amino acids into an isocyano group has resulted in a new class of N-urethane-protected amino isonitriles. All the isonitriles have been isolated as stable solids, purified, and completely characterized. A synthetic application of the obtained isonitriles has also been demonstrated through the synthesis of 1-substituted tetrazole analogues of amino acids via a 2 + 3 cycloaddition with trimethylsilyl azide.

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