Wang Yang, Shi Feng, Yao Xi-Xi, Sun Meng, Dong Liang, Tu Shu-Jiang
School of Chemistry and Chemical Engineering, Jiangsu Normal University, Xuzhou, 221116 (P. R. China), Fax: (+86) 516-83500065.
Chemistry. 2014 Nov 10;20(46):15047-52. doi: 10.1002/chem.201403868. Epub 2014 Sep 26.
The first catalytic asymmetric construction of a spirooxindole scaffold incorporated with a seven-membered benzodiazepine moiety has been established by a three-component (isatin, 1,2-phenylenediamine, cyclohexane-1,3-dione) tandem reaction catalyzed by a chiral phosphoric acid. Structurally complex spirobenzodiazepine oxindoles with one quaternary stereogenic center are obtained in high yield with excellent enantioselectivity (up to 99% yield, enantiomeric ratio>99.5:0.5). This approach takes advantage of organocatalytic asymmetric tandem reactions to efficiently construct the structurally rigid spirobenzodiazepine oxindole architecture with high enantiopurity in a single transformation, which involves a cascade enamine-imine formation/intramolecular Mannich reaction sequence.
在手性磷酸催化的三组分（异吲哚酮、1,2 - 苯二胺、环己烷 - 1,3 - 二酮）串联反应中，首次实现了含有七元苯并二氮杂䓬部分的螺环氧化吲哚骨架的催化不对称构建。具有一个季碳立体中心的结构复杂的螺环苯并二氮杂䓬氧化吲哚以高收率和优异的对映选择性得到（收率高达99%，对映体比例>99.5:0.5）。该方法利用有机催化不对称串联反应，通过单一转化高效构建具有高对映纯度的结构刚性螺环苯并二氮杂䓬氧化吲哚结构，这涉及烯胺 - 亚胺形成/分子内曼尼希反应序列的串联。
