通过支链三炔的[2 + 2 + 2]环加成反应对映选择性合成手性三脚架笼状化合物。

Enantioselective synthesis of chiral tripodal cage compounds by [2 + 2 + 2] cycloaddition of branched triynes.

作者信息

Shibata Takanori, Uchiyama Toshifumi, Endo Kohei

机构信息

Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, Okubo, Shinjuku, Tokyo 169-8555, Japan.

出版信息

Org Lett. 2009 Sep 3;11(17):3906-8. doi: 10.1021/ol9014893.

DOI:10.1021/ol9014893

PMID:19663465

Abstract

Cyclotrimerization of triynes branched by a nitrogen atom of 2-aminophenol yielded planar-chiral tripodal cage compounds. When a cationic Rh-Me-DUPHOS catalyst was used, the cycloadducts were obtained in high yield and excellent ee, and a macrocyclic compound with a [15]cyclophane system was also obtained. This method can be further applied to the synthesis of a triarmed pyridinophane by the intramolecular reaction of a diyne-nitrile.

摘要

由2-氨基苯酚的氮原子支化的三炔的环三聚反应生成了平面手性三脚架笼状化合物。当使用阳离子Rh-Me-DUPHOS催化剂时，环加成产物以高产率和优异的对映体过量获得，并且还得到了具有[15]环芳体系的大环化合物。该方法可进一步应用于通过二炔腈的分子内反应合成三臂吡啶并环芳烃。