环己烷-1,3-二酮与吡啶𬭩盐的串联亲核环化反应。
Tandem dinucleophilic cyclization of cyclohexane-1,3-diones with pyridinium salts.
机构信息
Institut für Chemie der Universität Rostock, Albert-Einstein-Straße 3a, D-18059 Rostock, Germany, ; Laboratory of Organic Synthesis and Natural Products, Department of Chemistry, Sharif University of Technology, P. O. Box 11155-9516 Tehran, Iran ; Department of Chemistry, Faculty of Science, University of Qom, Qom, Iran.
出版信息
Beilstein J Org Chem. 2013 Jun 10;9:1119-26. doi: 10.3762/bjoc.9.124. Print 2013.
The cyclization of cyclohexane-1,3-diones with various substituted pyridinium salts afforded functionalized 8-oxa-10-aza-tricyclo[7.3.1.0(2,7)]trideca-2(7),11-dienes. The reaction proceeds by regioselective attack of the central carbon atom of the 1,3-dicarbonyl unit to 4-position of the pyridinium salt and subsequent cyclization by base-assisted proton migration and nucleophilic addition of the oxygen atom to the 2-position, as was elucidated by DFT computations. Fairly extensive screening of bases and additives revealed that the presence of potassium cations is essential for formation of the product.
各种取代的吡啶𬭩盐与环己烷-1,3-二酮的环化反应得到了功能化的 8-氧代-10-氮杂三环[7.3.1.0(2,7)]十三-2(7),11-二烯。该反应通过 1,3-二羰基单元的中心碳原子对吡啶𬭩盐的 4-位的区域选择性攻击，并通过碱辅助质子迁移和氧原子对 2-位的亲核加成进行后续环化，这一点通过 DFT 计算得到了阐明。对碱和添加剂的广泛筛选表明，钾阳离子的存在对于产物的形成是必不可少的。
Zotero 插件