Improved asymmetric SNAr reaction of β-dicarbonyl compounds catalyzed by quaternary ammonium salts derived from cinchona alkaloids
Improved asymmetric SNAr reaction of β-dicarbonyl compounds catalyzed by quaternary ammonium salts derived from cinchona alkaloids
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DOI：
10.1021/jo060627l
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发表时间：
2006-06-23
影响因子：
3.6
通讯作者：
Jorgensen, Karl Anker
中科院分区：
文献类型：
--
作者：
Kobbelgaard, Sara;Bella, Marco;Jorgensen, Karl Anker
介绍了N-苄基-O-苯甲酰基辛可宁或辛可尼盐类催化α-取代1，3-二羰基化合物与活性芳香族化合物的不对称亲核芳香取代反应的范围和局限性。合成了几种新型的邻苯甲酰金鸡纳生物碱衍生物盐，并评价了它们在该反应中的催化性能，其对映体选择性最高可达96%ee。考察了不同的1，3-二羰基化合物和活性芳香族体系对芳香族亲核取代反应的影响，发现反应的产率和对映体选择性与底物和试剂密切相关。报道了产物的官能化范围，如螺氧吲哚，1，3α，α二取代二羰基化合物与几种亲核试剂的开环反应，以及光学活性SNAR产品中酮基官能团的非对映选择性还原。
The scope and limitation of the asymmetric nucleophilic aromatic substitution reaction of alpha-substituted 1,3-dicarbonyl compounds and activated aromatic systems catalyzed by N-benzyl-O-benzoylcinchoninium or cinchonidinium salts are presented. Several novel O-benzoylcinchona alkaloid derived salts have been prepared and evaluated as catalysts in this reaction, which can proceed with enantioselectivites up to 96% ee. Various 1,3-dicarbonyl compounds and activated aromatic systems are evaluated for the aromatic nucleophilic substitution reaction, and it has been found that the yield and enantioselectivity are very dependent on the substrate and reagent. The scope of the functionalization of the products to, e. g., spirooxoindole, a ring-opening reaction of 1,3 alpha, alpha-disubstituted dicarbonyl compounds with several nucleophiles, and the diastereoselective reduction of the keto functionality in the optically active SNAr product are reported.