Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, Sauvage Center for Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, People's Republic of China.
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen 518000, People's Republic of China.
Org Biomol Chem. 2020 Feb 7;18(5):856-859. doi: 10.1039/c9ob02536g. Epub 2020 Jan 15.
A highly enantioselective hydrogenation of exocyclic α,β-unsaturated carbonyl compounds catalyzed by Rh/bisphosphine-thiourea (ZhaoPhos) has been developed, giving the corresponding α-chiral cyclic lactones, lactams and ketones with high yields and excellent enantioselectivities (up to 99% yield and 99% ee). Remarkably, the hydrogen bond between the substrate and the catalyst plays a critical role in this transformation. The synthetic utility of this protocol has been demonstrated by efficient synthesis of chiral 3-(4-fluorobenzyl)piperidine, a key chiral fragment of bioactive molecules.
已开发出一种由 Rh/双膦-硫脲（ZhaoPhos）催化的高度对映选择性的外消旋α,β-不饱和羰基化合物的氢化反应，可高收率和优异对映选择性（高达 99%的收率和 99%的对映体过量）得到相应的α-手性环状内酯、内酰胺和酮。值得注意的是，底物和催化剂之间的氢键在这种转化中起着关键作用。该方案的合成实用性已通过生物活性分子的关键手性片段 3-(4-氟苄基)哌啶的高效合成得到证明。
