| 苗晓,李海峰,逄增波,王来来.D-甘露醇衍生的手性亚磷酸酯配体：合成及应用于铑催化α-脱氢氨基酸酯不对称氢化[J].分子催化,2014,(5):393-399 |
| D-甘露醇衍生的手性亚磷酸酯配体：合成及应用于铑催化α-脱氢氨基酸酯不对称氢化 |
| Chiral Diphosphite Ligands Derived from D-mannitol: Synthesis and Their Application in the Rh-Catalyzed Enantioselective Hydrogenation of α-Dehydroamino Acid Esters |
| 投稿时间：2014-06-26 修订日期：2014-09-09 |
| DOI： |
| 中文关键词: 双齿亚磷酸酯 铑络合物 α-脱氢氨基酸酯 不对称氢化反应 |
| 英文关键词:Diphosphites Rh-complex α-Dehydroamino acid esters Asymmetric hydrogenation |
| 基金项目:国家自然科学基金项目（面上项目，重点项目，重大项目） |
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| 中文摘要: |
| 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. |
| 英文摘要: |
| A new tropos ligand based on the 1,2:5,6-di-O-cyclohexylidene-D-mannitol and 2,2’-dihydroxybiphenyl was easily synthesized. And some chiral diphosphite ligands based on D-mannitol derivatives were also prepared. They were all successfully applied to the Rh-catalyzed asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate(5a) and methyl (Z)-2-benzoylamidocinnamate(5b). The effect of ligand structure, solvent and the ratio of substrate/catalyst on enantioselectivity were examined. The stereochemically matched combination of 1,2:5,6-di-O-isopropylidene-D-mannitol and (R)-binaphthyl was essential to afford 93.5% ee for the hydrogenation of 5a. Hydrogenation of α-dehydroamino acid esters with electron-donating substituents on the phenyl ring gave higher enantioselectivity than those with electron-withdrawing substituents, no matter these substituents are at the ortho or para position of the phenyl ring. |
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