轴手性2,2'-联吡啶衍生物的合成、表征与催化性质研究
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摘要
轴手性2, 2'-联吡啶衍生物具有性质稳定、反应条件温和、易于制备等优点,因此被广泛应用于复杂分子的合成及不对称催化等领域。本文设计合成了一系列轴手性2, 2'-联吡啶衍生物L1-L4,通过~1H NMR、~(13)C NMR、X-射线单晶衍射对其组成和结构进行了表征。该类轴手性2,2'-联吡啶衍生物与Pd(II)形成的配合物,能有效催化2-环己烯-1-酮与芳基硼酸的不对称1, 4-加成反应,目标产物具有较好的对映选择性和高达94%的产率。
Due to its stability, mild reaction condition and easy preparation, 2, 2'-bipyridyl derivatives have been wide applied in organic synthesis and transition metal catalysis. In this paper, a series of axially chiral 2, 2'-bipyridine derivatives L1-L4 were synthesized and characterized by ~1H NMR, ~(13)C NMR, X-ray single crystal diffraction. Furthermore, the Pd(II) complexes with the axially chiral 2, 2'-bipyridine derivatives were applied in the asymmetric catalysis of 1,4-addition of 2-cyclohexen-1-one with arylboronic acid, affording the products with good enantioselectivities and high yields.
Due to its stability, mild reaction condition and easy preparation, 2, 2'-bipyridyl derivatives have been wide applied in organic synthesis and transition metal catalysis. In this paper, a series of axially chiral 2, 2'-bipyridine derivatives L1-L4 were synthesized and characterized by ~1H NMR, ~(13)C NMR, X-ray single crystal diffraction. Furthermore, the Pd(II) complexes with the axially chiral 2, 2'-bipyridine derivatives were applied in the asymmetric catalysis of 1,4-addition of 2-cyclohexen-1-one with arylboronic acid, affording the products with good enantioselectivities and high yields.
引文
[1]Christian Kaes, Alexander Katz, Mir Wais Hosseini. Bipyridine:The Most Widely Used Ligand. A Review of Molecules Comprisingat Least Two 2,2′-Bipyridine Units[J]. Chem. Rev., 2000, 100:3553-3590.
[2]Jung-Suk Choi, Joseph J. Braymer, Ayyalusamy Ramamoorthyb, Mi Hee Lim.DesignofSmallMoleculesThatTargetMetal-AΒSpeciesand Regulate Metal-Induced AΒAggregation and Neurotoxicity[J]. PNAS,2010, 107:21990-21995.
[3]Yonghwan Ji, Hyuck Jin Lee, Minjeong Kim, Geewoo Nam, Jaeheung Cho,MiHeeLim.StrategicDesignof2,2′-BipyridineDerivativesto ModulateMetal-Amyloid-βAggregation[J].Inorg.Chem.,2017,56:6695-6705.
[4]IdrissBedja,PrashantV.Kamat,XiaoHua,A.G.Lappin,Surat Hotchandani.PhotosensitizationofNanocrystallineZn OFilmsby Bis(2,2′-bipyridine)(2,2′-bipyridine-4,4′-dicarboxylicacid)ruthenium(II)[J]. Langmuir, 1997, 13, 2398-2403.
[5]Shaohui Lin, Xiyan Lu. Cationic Pd(II)/Bipyridine-Catalyzed Conjugate AdditionofArylboronicAcidstoβ,β-DisubstitutedEnones:ConstructionofQuaternaryCarbonCenters[J].Org.Lett.,2010,12:2536.
[6]Xiang Gao, Bo Wu, Wen-Xue Huang, Mu-Wang Chen, Yong-Gui Zhou.Enantioselective Palladium-Catalyzed C-H Functionalization of Indoles Using an Axially Chiral 2,2’-Bipyridine Ligand[J]. Angew. Chem. Int.Ed., 2015, 54:11956-11960.
[2]Jung-Suk Choi, Joseph J. Braymer, Ayyalusamy Ramamoorthyb, Mi Hee Lim.DesignofSmallMoleculesThatTargetMetal-AΒSpeciesand Regulate Metal-Induced AΒAggregation and Neurotoxicity[J]. PNAS,2010, 107:21990-21995.
[3]Yonghwan Ji, Hyuck Jin Lee, Minjeong Kim, Geewoo Nam, Jaeheung Cho,MiHeeLim.StrategicDesignof2,2′-BipyridineDerivativesto ModulateMetal-Amyloid-βAggregation[J].Inorg.Chem.,2017,56:6695-6705.
[4]IdrissBedja,PrashantV.Kamat,XiaoHua,A.G.Lappin,Surat Hotchandani.PhotosensitizationofNanocrystallineZn OFilmsby Bis(2,2′-bipyridine)(2,2′-bipyridine-4,4′-dicarboxylicacid)ruthenium(II)[J]. Langmuir, 1997, 13, 2398-2403.
[5]Shaohui Lin, Xiyan Lu. Cationic Pd(II)/Bipyridine-Catalyzed Conjugate AdditionofArylboronicAcidstoβ,β-DisubstitutedEnones:ConstructionofQuaternaryCarbonCenters[J].Org.Lett.,2010,12:2536.
[6]Xiang Gao, Bo Wu, Wen-Xue Huang, Mu-Wang Chen, Yong-Gui Zhou.Enantioselective Palladium-Catalyzed C-H Functionalization of Indoles Using an Axially Chiral 2,2’-Bipyridine Ligand[J]. Angew. Chem. Int.Ed., 2015, 54:11956-11960.