双环[3.3.1]壬-3-烯-2-酮的合成与化学多样性分析
Synthesis and chemical diversity analysis of bicyclo[3.3.1]non-3-en-2-ones.
作者信息
Hammill Jared T, Contreras-García Julia, Virshup Aaron M, Beratan David, Yang Weitao, Wipf Peter
机构信息
Center for Chemical Methodologies and Library Development, University of Pittsburgh, Pittsburgh, PA 15260, USA.
出版信息
Tetrahedron. 2010 Mar 31;66(31):5852-5862. doi: 10.1016/j.tet.2010.04.112.
Abstract
Functionalized bicyclo[3.3.1]non-3-en-2-ones are obtained from commercially available phenols by a hypervalent iodine oxidation, enone epoxidation, epoxide thiolysis, and intramolecular aldol reaction sequence. Reaction optimization studies identified room temperature as well as microwave-mediated procedures, providing moderate to good yields (57%-88%) in the thiophenol-mediated epoxide opening and intramolecular aldol reaction. In addition, the isolation of a key intermediate and in situ NMR studies supported the mechanistic hypothesis. The bicyclic ring products occupy novel chemical space according to ChemGPS and Chemaxon chemical diversity and cheminformatics analyses.
摘要
功能化的双环[3.3.1]壬-3-烯-2-酮可通过高价碘氧化、烯酮环氧化、环氧化物硫解和分子内羟醛缩合反应序列，从市售酚类化合物制得。反应优化研究确定了室温以及微波介导的方法，在硫酚介导的环氧化物开环和分子内羟醛缩合反应中提供了中等至良好的产率（57%-88%）。此外，关键中间体的分离和原位核磁共振研究支持了机理假设。根据ChemGPS和Chemaxon化学多样性及化学信息学分析，双环产物占据了新的化学空间。
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