Beller M, Breindl C, Riermeier T H, Tillack A
Institut für Organische Katalyseforschung an der Universität Rostock e. V., Buchbinderstrasse 5-6, 18055 Rostock, Germany.
J Org Chem. 2001 Feb 23;66(4):1403-12. doi: 10.1021/jo001544m.
Aliphatic and aromatic amines react with 2- and 3-chlorostyrene in the presence of potassium tert-butoxide to give N-substituted 2,3-dihydroindoles in good yields. The combination of this domino-amination protocol with a suitable dehydrogenation reaction gives access to pharmacologically interesting indoles in a one-pot procedure. Overall product yields of N-substituted indoles >50% are obtained by this method starting from commercially available substrates. In addition to the intramolecular base-promoted amination of aromatic C-Cl bonds, metal-free intermolecular aminations of aryl chlorides with primary and secondary amines are described. The use of potassium tert-butoxide as base allows the synthesis of various anilines in good to excellent yields. Due to the formation of aryne intermediates, either N-substituted anilines or meta-substituted anilines are produced with excellent selectivities.
脂肪族和芳香族胺在叔丁醇钾存在下与2-氯苯乙烯和3-氯苯乙烯反应，以良好的产率得到N-取代的2,3-二氢吲哚。这种多米诺胺化反应方案与合适的脱氢反应相结合，能够通过一锅法获得具有药理活性的吲哚。从市售底物出发，通过该方法可得到产率大于50%的N-取代吲哚。除了分子内碱促进的芳族C-Cl键胺化反应外，还描述了芳基氯化物与伯胺和仲胺的无金属分子间胺化反应。使用叔丁醇钾作为碱能够以良好至优异的产率合成各种苯胺。由于芳炔中间体的形成，能够以优异的选择性生成N-取代苯胺或间位取代苯胺。
