Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
J Am Chem Soc. 2010 Jun 30;132(25):8550-1. doi: 10.1021/ja1033952.
A general solution for the synthesis of various oxetan-3-ones is developed. This reaction uses readily available propargylic alcohols as substrates and proceeds without the exclusion of moisture or air ("open flask"). Notably, oxetan-3-one, a highly valuable substrate for drug discovery, can be prepared in one step from propargyl alcohol in a fairly good yield. The facile formation of the strained oxetane ring provides strong support for the intermediacy of alpha-oxo gold carbenes. This safe and efficient generation of gold carbenes via intermolecular alkyne oxidation offers a potentially general entry into alpha-oxo metal carbene chemistry without using hazardous diazo ketones.
发展了一种合成各种环氧乙烷-3-酮的通用方法。该反应以易得的丙炔醇为底物,在不排除水分或空气的情况下进行(“开瓶”)。值得注意的是,环氧乙烷-3-酮是药物发现中非常有价值的底物,可以从丙炔醇一步以相当好的产率制备。刚性氧杂环丁烷环的易于形成为α-氧代金卡宾的中间体提供了有力支持。通过分子间炔烃氧化安全高效地生成金卡宾,为不使用危险的重氮酮进入α-氧代金属卡宾化学提供了一种潜在的通用方法。