Synthesis and Reactivity of a Terminal 1-Alkynyl Triazene.

1-Alkynyl triazenes are versatile reagents in synthetic organic chemistry, but the structural diversity of this compound class has so far been limited. Herein, we describe the synthesis of a terminal 1-alkynyl triazene. Subsequent functionalization allows the preparation of 1-alkynyl triazenes with a range of functional groups including esters, alcohols, cyanides, phosphonates, and amides. Furthermore, the terminal 1-alkynyl triazene can be used for the synthesis of di- and triynes and for the preparation of (hetero)aromatic triazenes in metal-catalyzed cyclization reactions.

Divergent Synthesis of Densely Substituted Arenes and Pyridines via Cyclotrimerization Reactions of Alkynyl Triazenes.

Densely substituted fused aromatic triazenes can be prepared by [2 + 2 + 2] cyclotrimerization reactions of 1-alkynyl triazenes. The Cp*Ru-catalyzed cyclization proceeds well with both simple alkynyl triazenes and tethered 1-diynyl triazenes. Attractively, the methodology can be extended to pyridine synthesis by replacing an alkyne with a nitrile. The reaction is regioselective and yields the sterically more hindered product. The triazene group precisely installed on the synthesized aryl and pyridyl ring is a highly versatile moiety, which is effortlessly converted into the most important and frequently used functional aryl substituents, including fluorides. It is also suited for intramolecular transformations to afford a variety of valuable heterocycles. The coordination chemistry of alkynyl triazenes and Cp*RuCl was studied and led to the structural characterization of a Cp*RuCl(η2-alkyne) complex, a Cp*RuCl(η4-cyclobutadiene) complex, and an unusual dinuclear Ru complex with a bridging tetramethylfulvene ligand. Complexes of this type are potentially involved in catalyst deactivation pathways.