Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways.
Phosphine-catalyzed annulations of azomethine imines: allene-dependent [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] pathways.
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DOI：
10.1021/ja200231v
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发表时间：
2011-08-31
影响因子：
15
通讯作者：
Kwon, Ohyun
中科院分区：
文献类型：
--
作者：
Na, Risong;Jing, Chengfeng;Xu, Qihai;Jiang, Hui;Wu, Xi;Shi, Jiayan;Zhong, Jiangchun;Wang, Min;Benitez, Diego;Tkatchouk, Ekaterina;Goddard, William A., III;Guo, Hongchao;Kwon, Ohyun
在这篇论文中，我们描述了膦催化的[3+2]，[3+3]，[4+3]和[3+2+3]甲亚胺和联烯丙酸酯的环化反应。这些方法标志着甲亚胺在亲核膦催化中的首次使用，产生了二氮稠合杂环，包括四氢吡唑并吡唑酮、-哒嗪酮、-二氮杂环酮和-重氮酮。考虑到[3+3]环化反应中的两种不同反应模式，有五条不同的反应路径--选择哪条路径取决于烯丙酸酯的结构和化学性质。所有反应操作简单，在温和的反应条件下顺利进行，以中等至优异的产率提供了广泛的1，2-二氮杂环。由一个膦和两个2，3-丁二烯酸乙酯分子形成的两性中间体在甲亚胺的环上作为1，5-偶极，生成[3+2+3]四氢吡唑重氮酮产物。将两个烯丙酸酯分子结合到一个八元环产品中，代表了这类用途广泛的分子在亲核膦催化中的新应用。该方法的显著特点是可以方便地获得多种含氮杂环，并且可以简单地制备甲亚胺底物，这表明它可能在杂环合成中得到广泛的应用。
In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways—the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen–containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolodiazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol—the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates—suggest that it might find extensive applications in heterocycle synthesis.
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影响因子：
3.2
作者：
Davies, SG;Rodríguez-Sola, H;Smith, AD
通讯作者：
Smith, AD
影响因子：
3.6
作者：
Córdova, A;Notz, W;Barbas, CF
通讯作者：
Barbas, CF
影响因子：
2.1
作者：
Creech, Gardner S.;Zhu, Xue-Feng;Foncivic, Branden;Dudding, Travis;Kwon, Ohyun
通讯作者：
Kwon, Ohyun
DOI：
10.1039/j39700001597
发表时间：
1970-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC
影响因子：
--
作者：
ARMAREGO, WL;KOBAYASHI, T
通讯作者：
KOBAYASHI, T
影响因子：
2.9
作者：
CUCUROU, C;BATTIONI, JP;MANSUY, D
通讯作者：
MANSUY, D