Wu Zhiyong, Isaac Kévin, Retailleau Pascal, Betzer Jean-François, Voituriez Arnaud, Marinetti Angela
Institut de Chimie des Substances Naturelles, ICSN - CNRS UPR 2301, Université Paris-Sud, Université Paris-Saclay, 1, av. de la Terrasse, 91198, Gif-sur-Yvette, France.
Chemistry. 2016 Mar 1;22(10):3278-3281. doi: 10.1002/chem.201504658. Epub 2016 Feb 2.
The key structural feature of the new phosphoramidites is a paracyclophane scaffold in which two aryl rings are tethered by both a 1,8-biphenylene unit and a O-P-O bridge. Suitable aryl substituents generate planar chirality. The corresponding gold(I) complexes promote the cycloisomerization of prochiral nitrogen-tethered dienynes. These reactions afford bicyclo[4.1.0]heptene derivatives displaying three contiguous stereogenic centers, with very high diastereoselectivity and up to 95 % ee.
新型亚磷酰胺的关键结构特征是对环芳烷骨架，其中两个芳基环通过一个1,8-亚联苯基单元和一个O-P-O桥连接。合适的芳基取代基产生平面手性。相应的金（I）配合物促进前手性氮连接的二烯炔的环异构化反应。这些反应生成具有三个相邻立体中心的双环[4.1.0]庚烯衍生物，具有非常高的非对映选择性和高达95%的对映体过量。
