The Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen 518000, PR China.
State Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon 999077, Hong Kong.
Molecules. 2019 Feb 12;24(3):643. doi: 10.3390/molecules24030643.
The synthesis of a new CF₃-containing stereogenic atropisomeric pair of ortho-disubstituted biphenyl scaffold is presented. The atropisomers are surprisingly conformationally stable for isolation. X-ray structures show that their stability comes from an intramolecular hydrogen bond formation from their two hydroxyl groups and renders the spatial arrangement of their peripheral CF₃ and CH₃ groups very different. The synthesized stereogenic scaffold proved to be effective in catalyzing the asymmetric -nitroso aldol reaction of enamine and nitrosobenzene. Compared to similar scaffolds without CF₃ groups, one of our atropisomer exhibits an increase in enantioselectivity in this reaction.
本文报道了一种新型含 CF₃ 的手性轴手性对映异构体邻位二取代联苯骨架的合成。令人惊讶的是，这些对映异构体在分离时具有惊人的构象稳定性。X 射线结构表明，它们的稳定性来自于两个羟基之间的分子内氢键形成，这使得它们外围 CF₃ 和 CH₃ 基团的空间排列非常不同。所合成的手性骨架被证明能有效地催化烯胺和亚硝基苯的不对称 - 亚硝基醇醛反应。与没有 CF₃ 基团的类似骨架相比，我们的一种对映异构体在该反应中表现出更高的对映选择性。
