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以1,2:5,6-双亚环己基-D-甘露醇为手性骨架,合成含有联苯基团的新型手性tropos配体;分别以1,2:5,6-双异丙叉-D-甘露醇和1,2:5,6-双亚环己基-D-甘露醇为原料,合成系列双齿亚磷酸酯配体,将这些配体应用于铑催化α-乙酰氨基肉桂酸甲酯5a和α-苯酰氨基肉桂酸甲酯5b氢化反应中,考察配体结构,溶剂,底物/催化剂的摩尔比对反应对映选择性的影响,优化了反应条件;在底物是α-乙酰胺基肉桂酸甲酯时,配体的双异丙叉骨架与(R)-联萘部分是匹配组合,反应对映选择性高达93.5%.在优化的反应条件下,尝试七个苯环含不同取代基团的底物,无论供电子基团在芳环的邻位还是对位,其氢化产物的对映选择性均高于相应位置为吸电子基团的.
A novel chiral tropos ligand containing biphenyl groups was synthesized with 1,2: 5,6-cyclohexylidene-D-mannitol as chiral backbone. F-D-mannitol and 1,2: 5,6-dicyclohexylidene-D-mannitol, a series of bidentate phosphite ligands were synthesized and applied to rhodium-catalyzed α-acetamidocinnamic acid Methyl ester 5a and α-benzoylaminocinnamate 5b hydrogenation reaction, the ligand structure, solvent, substrate / catalyst molar ratio on the reaction enantioselectivity, optimizing the reaction conditions; in the substrate is α-acetamidomethyl cinnamate, the double isopropylidene skeleton of the ligand and (R) -binaphthyl moiety is a matching combination, the reaction enantioselectivity up to 93.5% under the optimized reaction conditions, trying seven The benzene ring containing different substituents of the substrate, regardless of the electron donor group in the aromatic ring ortho or para, the hydrogenation product enantioselectivity than the corresponding position for the electron-withdrawing group.