Xie Liyu, Yang Haijian, Ma Mingliang, Xing Dong
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
Org Lett. 2020 Mar 6;22(5):2007-2011. doi: 10.1021/acs.orglett.0c00375. Epub 2020 Feb 17.
Herein, we report the first direct branched-selective α-allylic alkylation of simple ketones with alkynes under rhodium and secondary amine cooperative catalysis. Through a rhodium-hydride-catalyzed allylic substitution pathway, a series of valuable γ,δ-unsaturated ketones are obtained with excellent regioselectivity in an atom-economic and byproduct-free manner. With a chiral BIPHEP ligand, high enantioselectivity has been achieved for this transformation.
在此，我们报道了在铑和仲胺协同催化下，简单酮与炔烃的首例直接支链选择性α-烯丙基烷基化反应。通过铑氢催化的烯丙基取代途径，以原子经济且无副产物的方式，高区域选择性地得到了一系列有价值的γ,δ-不饱和酮。使用手性BIPHEP配体，该转化反应实现了高对映选择性。
