Max-Planck-Institut für Kohlenforschung, 45470 Mülheim/Ruhr, Germany.
J Am Chem Soc. 2021 Sep 29;143(38):15538-15555. doi: 10.1021/jacs.1c08040. Epub 2021 Sep 14.
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 and W NMR spectroscopy. The remaining shortcomings, gaps, and desiderata in the field are also critically assessed.
由于具有众多的有利特性和战略优势，当代炔烃复分解反应越来越被认为是一种强大的合成工具。这一发展的核心是过去几十年中催化剂的显著演变。带有（三脚形）硅醇盐配体的钼烷基炔烃目前设定了标准；它们的官能团兼容性非常出色，尽管它们包含处于最高氧化态的早期过渡金属。它们的性能在动态共价化学领域的案例研究、对固相合成的高级应用、环反应的复兴以及复杂靶分子在特定位置的组装中得到了体现，而这些位置可能不会直观地追溯到炔烃的祖先。与这些材料科学和有机合成方面的创新并行的是，通过计算手段和使用非常规分析工具（如 Mo 和 W NMR 光谱学），对最先进催化剂的作用模式有了新的认识。该领域中仍存在的缺点、差距和期望也受到了严格评估。
