Dual-function cinchona alkaloid catalysis: Catalytic asymmetric tandem conjugate addition-protonation for the direct creation of nonadjacent stereocenters
Dual-function cinchona alkaloid catalysis: Catalytic asymmetric tandem conjugate addition-protonation for the direct creation of nonadjacent stereocenters
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DOI：
10.1021/ja060312n
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发表时间：
2006-03-29
影响因子：
15
通讯作者：
Deng, L
中科院分区：
文献类型：
--
作者：
Wang, Y;Liu, XF;Deng, L
催化串联不对称反应是直接从非手性前体在无环分子中不对称构建非相邻立构中心的有力策略。在这篇通讯中，我们报告了一个高的对映选择性和非对映选择性的加成三取代碳供体2-氯丙烯腈催化的双功能金鸡纳生物碱催化剂。这代表了第一个不对称串联共轭加成-质子化反应，有效地催化控制了两个不相邻的立体中心。正如在（−）-manzacidin A的简洁和高度立体选择性的形式全合成中所证明的那样，这种不对称串联反应建立了一种新的和通用的催化方法，用于对映选择性和非对映选择性地产生1，3-叔-季立体中心。
Catalytic tandem asymmetric reactions constitute a powerful strategy for the asymmetric construction of nonadjacent stereocenters in acyclic molecules directly from achiral precursors. In this Communication, we report a highly enantioselective and diastereoselective addition of trisubstituted carbon donors to 2-chloroacrylonitrile catalyzed by bifunctional cinchona alkaloid catalysts. This represents the first asymmetric tandem conjugate addition−protonation with efficient catalytic control of two nonadjacent stereocenters. As demonstrated in a concise and highly stereoselective formal total synthesis of (−)-manzacidin A, this asymmetric tandem reaction establishes a new and versatile catalytic approach for the enantioselective and diastereoselective creation of 1,3-tertiary−quaternary stereocenters.