作者:Rudy Lhermet、Alois Fürstner
DOI:10.1002/chem.201404166
日期:2014.10.6
Terminal acetylenes are amongst the most problematic substrates for alkyne metathesis because they tend to undergo rapid polymerization on contact with a metal alkylidyne. The molybdenum complex 3 endowed with triphenylsilanolate ligands, however, is capable of inducing surprisingly effective cross‐metathesis reactions of terminal alkyl acetylenes with propynyl(trimethyl)silane to give products of
末端乙炔是炔烃复分解中最成问题的底物之一,因为它们在与金属亚烷基接触时趋于快速聚合。钼络合物3赋予triphenylsilanolate配体,但是,是能够诱导末端烷基乙炔的令人惊讶地有效的交叉复分解反应与丙炔基(三甲基)硅烷,得到R型的产品的1 CCSiMe。这种在甲炔基末端引入甲硅烷基取代基的非常规方法补充了传统的去质子化/硅烷化策略,并且非常适合作为具有碱敏功能的底物的炔烃保护基化学的正交方法。此外,结果表明,即使末端芳基乙炔也可以与内部炔烃伙伴交叉复分解。这些史无前例的转换与各种功能组兼容。还讨论了抑制乙炔形成的需求,这似乎是一种特别有效的催化剂毒物。