Liu Dan, Sun Jing, Xie Ju, Shi Huizhong, Yan Chao-Guo
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China.
J Org Chem. 2021 Jan 15;86(2):1827-1842. doi: 10.1021/acs.joc.0c02645. Epub 2021 Jan 2.
The three-component reaction of ,-unsaturated -arylaldimines, dialkyl but-2-ynedioates, and 2-arylidene Meldrum acids in DCM at room temperature gave mixtures of /-11-aryl-7-styryl-2,4-dioxa-8-azaspiro[5.5]undec-9-enes in satisfactory yields. The similar three-component reaction with 2-arylidene-,'-dimethylbarbituric acids afforded -11-phenyl-7-styryl-2,4,8-triazaspiro[5.5]undec-9-enes as major products. On the other hand, the three-component reaction of -arylaldimines, dialkyl but-2-ynedioates, and 2-arylidene Meldrum acids or 2-arylidene-,'-dimethylbarbituric acids afforded /isomeric spirocompounds in satisfactory yields with high diastereoselectivity. This domino [2+2+2] cycloaddition reaction proceeded with sequential nucleophilic addition of -arylaldimine to an electron-deficient alkyne, Michael addition, and annulation process. The stereochemistry of all / isomeric spirocompounds was clearly elucidated by the determination of 33 single-crystal structures. The diastereoselectivity of the three-component reaction was correlated by DFT calculations.
在室温下，α,β-不饱和芳基亚胺、丁-2-炔二酸二烷基酯和2-亚芳基丙二酸亚异丙酯在二氯甲烷中的三组分反应，以令人满意的产率得到了α/β-11-芳基-7-苯乙烯基-2,4-二氧杂-8-氮杂螺[5.5]十一碳-9-烯的混合物。与2-亚芳基-α,α'-二甲基巴比妥酸的类似三组分反应，以-11-苯基-7-苯乙烯基-2,4,8-三氮杂螺[5.5]十一碳-9-烯作为主要产物。另一方面，α-芳基亚胺、丁-2-炔二酸二烷基酯与2-亚芳基丙二酸亚异丙酯或2-亚芳基-α,α'-二甲基巴比妥酸的三组分反应，以高非对映选择性得到了令人满意产率的α/β-异构螺环化合物。这种多米诺[2+2+2]环加成反应通过α-芳基亚胺对缺电子炔烃的顺序亲核加成、迈克尔加成和环化过程进行。通过测定33个单晶结构，明确阐明了所有α/β-异构螺环化合物的立体化学。通过密度泛函理论计算关联了三组分反应的非对映选择性。
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