Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2018 Mar 1;57(10):2721-2725. doi: 10.1002/anie.201713329. Epub 2018 Feb 5.
A copper-catalyzed enantioselective arylative desymmetrization of prochiral cyclopentenes with diaryliodonium salts was developed. In the presence of a catalytic amount of a chiral copper-bisoxazoline complex, which was generated in situ, the reaction of 4-substituted or 4,4-disubstituted cyclopent-1-enes with diaryliodonium hexafluoroarsenates afforded the chiral arylated products in good yields with excellent enantioselectivity. A cyclohexyl-containing Box ligand was essential for the high enantioselectivity. Transformation of the enantiomerically enriched adducts into other chiral building blocks is also documented.
发展了一种铜催化的手性选择性芳基去对称化反应，用于带有二芳基碘鎓盐的前手性环戊烯。在催化量的手性铜-双恶唑啉配合物的存在下，该配合物原位生成，4-取代或 4,4-二取代的环戊-1-烯与二芳基碘六氟砷酸盐反应，以优异的对映选择性得到了手性芳基化产物，产率良好。含有环己基的 Box 配体对于高对映选择性是必不可少的。还记录了对映体富集加成物转化为其他手性构建块的情况。
