通过铜介导的2-氮杂-2,4-庚二烯-6-炔基阴离子环化反应合成氮杂环庚烷衍生物。有机铜中心对碳-碳三键的分子内加成反应。
Novel synthesis of azepine derivatives via copper-mediated cyclization of 2-aza-hepta-2,4-dien-6-ynyl anions. Intramolecular addition of organocopper centers to the C-C triple bond.
作者信息
Lyaskovskyy Volodymyr, Bergander Klaus, Fröhlich Roland, Würthwein Ernst-Ulrich
机构信息
Organisch-Chemisches Institut der Westfälischen Wilhelms-Universität Münster, D-48149 Münster, Germany.
出版信息
Org Lett. 2007 Mar 15;9(6):1049-52. doi: 10.1021/ol063081y. Epub 2007 Feb 14.
PMID:17298076
Abstract
Deprotonation of alkynyl imines 1 with LDA at low temperature and subsequent transmetalation with copper thiophenolate gives the annulated azepines 11a-i in 41-73% yield after aqueous workup. The key step of the reaction is a copper-mediated intramolecular nucleophilic attack at the triple bond. [reaction: see text]
摘要
在低温下用LDA使炔基亚胺1去质子化，随后与硫代苯酚铜进行转金属化反应，经水后处理后，以41 - 73%的产率得到稠合氮杂环庚三烯11a - i。该反应的关键步骤是铜介导的对三键的分子内亲核进攻。[反应：见正文]
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