Asymmetric Nazarov Reaction Catalyzed by Chiral Tris(oxazoline)/Copper(II)
Asymmetric Nazarov Reaction Catalyzed by Chiral Tris(oxazoline)/Copper(II)
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手性Tris(恶唑啉)/Copper(II)催化的不对称纳扎罗夫反应
DOI：
10.1002/anie.200907266
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Tang, Yong
中科院分区：
文献类型：
--
作者：
Cao, Peng;Deng, Chao;Tang, Yong
五元碳环化合物在天然产物和其他生物活性化合物中的频繁出现为开发有效的构建方法提供了主要动力。[1]为此，Nazarov环化，一种通过对旋环化将二乙烯基酮转化为环戊烯酮的立体特异性4π电环化，已经成为合成此类化合物的有力工具。[2]几十年来，人们一直致力于开发纳扎罗夫反应，[3]进一步突出了其合成实用性，正如其在全合成中的使用越来越多所证明的那样。[4]然而，直到2003年底才报道了催化量的手性源的不对称Nazarov反应，可能是由于该反应的复杂机理。[5]在所开发的那些催化不对称反应中，[5]除了属于类型A或B的二乙烯基酮（方案1）之外，很少有实例报道以良好的产率给出良好至优异的对映体控制。
The frequent occurrence of five-membered carbocycles in natural products and other biologically active compounds has provided a major impetus for the development of efficient methods for their construction.[1] Towards this end, the Nazarov cyclization, a stereospecific 4π electrocyclization that converts divinyl ketones into cyclopentenones through a conrotatory cyclization, has distinguished itself as a powerful tool for the synthesis of such compounds.[2] Over several decades, great efforts have been devoted to the exploitation of the Nazarov reaction,[3] further highlighting its synthetic utility, as demonstrated by its increasing use in total syntheses.[4] However, the asymmetric Nazarov reaction with a catalytic amount of chiral source was not reported until the end of 2003, probably because of the complex mechanism of the reaction.[5] Of those catalytic asymmetric reactions developed,[5] few examples have been reported that give good to excellent enantiocontrol in good yields, except for divinyl ketones that belong to type A or B (Scheme1).