From central to helical chirality:: Synthesis of P and M enantiomers of [5]helicenequinones and bisquinones from (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone

被引:83
作者
Carreño, MC [1 ]
García-Cerrada, S [1 ]
Urbano, A [1 ]
机构
[1] Univ Autonoma Madrid, Dept Quim Organ, E-28049 Madrid, Spain
关键词
asymmetric synthesis; cycloadditions; helical structures; quinones sulfoxides;
D O I
10.1002/chem.200304835
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of 1,4-divinyl-1,3-cyclohexadiene, 5,8-dimethoxy- or tert-butyldimethylsilyloxy-3-vinyl-1,2-dihydrophenanthrene or 6-vinyl-7,8-dihydro-1,4-phenanthrenequinone with an excess of enantiopure (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone (2) led to the direct formation of enantioenriched dihydro[5]helicenequinones or bisquinones (50 --> 98% ee). A domino Diels-Alder cycloaddition/sulfoxide elimination/partial aromatization process occurs, being the absolute configuration of the final helicene defined in the aromatization step. Both M and P helimers are accessible through a stepwise enantiodivergent process if the pentacyclic dihydroaromatic intermediate resulting in the two first steps is aromatized in the presence of (+/-)-2, DDQ, CAN or DBU.
引用
收藏
页码:4118 / 4131
页数:14
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