通过钯催化的邻炔基联芳基的5-外向-环化反应合成芴类化合物。
Synthesis of Fluorenes via the Palladium-Catalyzed 5-Exo-dig Annulation of o-Alkynyl Biaryls.
作者信息
Chernyak Natalia, Gevorgyan Vladimir
机构信息
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, ; phone: 312-355-3579;
出版信息
Adv Synth Catal. 2009 May 1;351(7-8):1101-1114. doi: 10.1002/adsc.200800765.
Abstract
The direct Pd-catalyzed intramolecular rapidly with electron-deficient benzene ring, which, in hydroarylation of o-alkynyl biaryls proceeded in highly combination with a substantial isotope effect observed, stereoselective manner producing fluorenes 2, the products of 5-exo-dig cyclization, in excellent yields. The cascade intermolecular arylation, incorporated in this transformation, allowed for efficient synthesis of fully-substituted fluorenes 12. These cyclizations proceed more rapidly with electron-deficient benzene ring, which, in combination with a substantial isotope effect observed, strongly supports a C-H activation mechanism for the key annulation step.
摘要
在缺电子苯环存在下，钯直接催化的邻炔基联芳基分子内氢芳基化反应能够快速进行，该反应以高度立体选择性的方式生成芴类化合物2（5-外向-双环化产物），产率优异，同时还观察到显著的同位素效应。此转化过程中包含的级联分子间芳基化反应，实现了全取代芴类化合物12的高效合成。这些环化反应在缺电子苯环存在下进行得更快，结合观察到的显著同位素效应，有力地支持了关键环化步骤的C-H活化机理。
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