Soluble polymeric chiral binaphthol （BINOL） ligands have been synthesized through copolymerization of 3,3′-bis（hydroxymethyl）-2,2′-bis（methoxymethy leneoxy）-1,1′-binaphthyl,1,6-dihydroxyhexane and 1,4-benzene...Soluble polymeric chiral binaphthol （BINOL） ligands have been synthesized through copolymerization of 3,3′-bis（hydroxymethyl）-2,2′-bis（methoxymethy leneoxy）-1,1′-binaphthyl,1,6-dihydroxyhexane and 1,4-benzene dicarbonyl chloride followed by deprotection of methoxymethyleneoxy groups by iPrOH/HCl,and their application in the enantioselective addition of diethylzinc to benzaldehyde was investigated.All soluble polymeric chiral BINOL ligands were characterized by IR、 1H-NMR、GPC and elemental analysis,which clearly demonstrated the formation of polymeric chiral BINOL ligands.These soluble polymeric chiral ligands were found to be effective in the addition of diethylzinc to benzaldehyde either in the presence or in the absence of Ti（Oi Pr）4 with higher catalytic activities and lower enantioselectivities.In the latter case,the dendritic chiral BINOL ligands showed much higher catalytic activity and a little higher enantioselectivity than BINOLs.展开更多
吡唑啉酮环化合物因具有生物药理活性等多种特性和用途,被认为是极具价值的结构基元之一,吡唑环上易形成氢键等特性使得药物分子中的吡唑啉酮结构能够发挥生理活性。合成了多种以3,3′-二羧酸-1,1′-联萘酚为手性骨架、结构上下对称的...吡唑啉酮环化合物因具有生物药理活性等多种特性和用途,被认为是极具价值的结构基元之一,吡唑环上易形成氢键等特性使得药物分子中的吡唑啉酮结构能够发挥生理活性。合成了多种以3,3′-二羧酸-1,1′-联萘酚为手性骨架、结构上下对称的新型多活性中心C_(2)轴手性氢键型双酰基硫脲催化剂,将其用于催化合成吡唑啉酮衍生物。实验结果表明:在35℃下,以10 mol%(R)-N_(3),N_(3)′-双(4-甲基苯乙基)-2,2′-二羟基-[1,1′-联萘]-3,3′-二甲酰基硫脲为催化剂,底物物质的量比为1∶1.5,于10 mL CH_(2)Cl_(2)溶剂中回流反应24 h后,目标产物吡唑啉酮获得了良好的产率(89%)及e.e.值(91%),并对底物进行了扩展,其范围较广,有较好的普适性。展开更多
文摘Soluble polymeric chiral binaphthol （BINOL） ligands have been synthesized through copolymerization of 3,3′-bis（hydroxymethyl）-2,2′-bis（methoxymethy leneoxy）-1,1′-binaphthyl,1,6-dihydroxyhexane and 1,4-benzene dicarbonyl chloride followed by deprotection of methoxymethyleneoxy groups by iPrOH/HCl,and their application in the enantioselective addition of diethylzinc to benzaldehyde was investigated.All soluble polymeric chiral BINOL ligands were characterized by IR、 1H-NMR、GPC and elemental analysis,which clearly demonstrated the formation of polymeric chiral BINOL ligands.These soluble polymeric chiral ligands were found to be effective in the addition of diethylzinc to benzaldehyde either in the presence or in the absence of Ti（Oi Pr）4 with higher catalytic activities and lower enantioselectivities.In the latter case,the dendritic chiral BINOL ligands showed much higher catalytic activity and a little higher enantioselectivity than BINOLs.
文摘吡唑啉酮环化合物因具有生物药理活性等多种特性和用途,被认为是极具价值的结构基元之一,吡唑环上易形成氢键等特性使得药物分子中的吡唑啉酮结构能够发挥生理活性。合成了多种以3,3′-二羧酸-1,1′-联萘酚为手性骨架、结构上下对称的新型多活性中心C_(2)轴手性氢键型双酰基硫脲催化剂,将其用于催化合成吡唑啉酮衍生物。实验结果表明:在35℃下,以10 mol%(R)-N_(3),N_(3)′-双(4-甲基苯乙基)-2,2′-二羟基-[1,1′-联萘]-3,3′-二甲酰基硫脲为催化剂,底物物质的量比为1∶1.5,于10 mL CH_(2)Cl_(2)溶剂中回流反应24 h后,目标产物吡唑啉酮获得了良好的产率(89%)及e.e.值(91%),并对底物进行了扩展,其范围较广,有较好的普适性。
