A novel and efficient stereo-controlled synthesis of hexahydroquinolinones via the diene-transmissive hetero-Diels-Alder reaction of cross-conjugated azatrienes with ketenes and electrophilic dienophiles
A novel and efficient stereo-controlled synthesis of hexahydroquinolinones via the diene-transmissive hetero-Diels-Alder reaction of cross-conjugated azatrienes with ketenes and electrophilic dienophiles
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DOI：
10.1016/j.tet.2008.10.090
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发表时间：
2009-01-24
期刊：
影响因子：
2.1
通讯作者：
Saito, Takao
中科院分区：
文献类型：
--
作者：
Kobayashi, Satoru;Semba, Tomomi;Saito, Takao
研究了具有n -芳基、n -烷基、n -二甲氨基取代基的交叉共轭阿扎特啉（二酰亚胺或五-1,4-二酰亚胺）的二烯传递异二酰亚胺（DTHDA）反应。扎特丽烯与二苯基烯在室温下初始反应生成[2+2]环加合物的β -内酰胺，加热后进行[1,3]-异位重排生成正式的[4+2]环加合物。N-苯扎三烯与二甲基烯酮或二氯烯酮反应只生成[2+2]环加合物，而N-（二甲氨基）扎三烯与二氯烯反应不加热生成[4+2]环加合物。当[2+2]环加合物在β -内酰胺环的C-4上有两个不同的乙烯基取代基时，重排的区域选择性取决于空间因素和取代基的电子需求。初始[4+2]环加合物与缺电子亲二烯试剂（TONE， n-苯基马来酰亚胺）的第二次Diels-Alder反应立体选择性地生成了六氢喹啉酮衍生物。同样，aza-DTHDA反应的串联分子间-分子内模式以区域和立体选择性的方式产生了四环含氮杂环。(c) 2008 Elsevier Ltd.版权所有。
The diene-transmissive hetero-Diels-Alder (DTHDA) reactions of cross-conjugated azatrienes (divinylimines or penta-1,4-dies-3-imines) having an N-aryl, N-alkyl, OF N-dimethylamino substituent have been examined. The initial reaction of the azatrienes with diphenylketene at room temperature yielded beta-lactams of [2+2] cycloadducts, which upon heating underwent [1,3]-sigmatropic rearrangement to produce the formal [4+2] cycloadducts. The reaction of N-phenylazatriene with dimethylketene or dichloroketene produced the [2+2] cycloadducts only, while the reaction of N-(dimethylamino)azatriene with dichloroketene gave the [4+2] cycloadduct without heating. When the [2+2] cycloadduct has two different vinyl substituents at C-4 of the beta-lactam ring, the regioselectivity of the rearrangement depends on steric factors and the electronic demand of the substituents. The second Diels-Alder reaction of the initial [4+2] cycloadducts with electron-deficient dienophiles (TONE, N-phenylmaleimide) stereo-selectively yielded hexahydroquinolinone derivatives. Similarly, a tandem intermolecular-intramolecular mode of the aza-DTHDA reactions produced tetracyclic nitrogen-containing heterocycles in a regio- and stereoselective manner. (c) 2008 Elsevier Ltd. All rights reserved.