The Ascent of Alkyne Metathesis to Strategy-Level Status

For numerous enabling features and strategic virtues, contemporary alkyne metathesis is increasingly recognized as a formidable synthetic tool. Central to this development was the remarkable evolution of the catalysts during the past decades. Molybdenum alkylidynes carrying (tripodal) silanolate ligands currently set the standards; their functional group compatibility is exceptional, even though they comprise an early transition metal in its highest oxidation state. Their performance is manifested in case studies in the realm of dynamic covalent chemistry, advanced applications to solid-phase synthesis, a revival of transannular reactions, and the assembly of complex target molecules at sites, which one may not intuitively trace back to an acetylenic ancestor. In parallel with these innovations in material science and organic synthesis, new insights into the mode of action of the most advanced catalysts were gained by computational means and the use of unconventional analytical tools such as Mo-90 and W-1(83) NMR spectroscopy. The remaining shortcomings, gaps, and desiderata in the field are also critically assessed.

Automated summary

Contemporary alkyne metathesis is increasingly recognized as a formidable synthetic tool due to numerous enabling features and strategic virtues. The evolution of catalysts, particularly molybdenum alkylidynes carrying silanolate ligands, has set high standards with exceptional functional group compatibility. The performance of these catalysts has been demonstrated in various applications, including dynamic covalent chemistry and solid-phase synthesis, with new insights obtained through computational methods and unconventional analytical tools.