手性Salen-Co(Ⅱ)配合物催化芳香酮不对称还原反应研究I

目前,以廉价的氢气为氢源,由潜手性的酮不对称加氢是制备手性醇最好的方法之一[1].但存在手性催化剂的膦配体不稳定以及贵金属(Ru、 Rh)的流失等问题.硼氢化钠是一种较温和的氢化试剂,Mukaiyama等用具有C2对称轴的一系列光学活性的二亚胺钴配合物催化硼氢化钠不对称还原芳香酮,实现了以硼氢化钠为氢源的不对称氢化反应[2].     

手性Salen—Co（Ⅱ）配合物催化芳香酮不对称还原反应研究

目前,以廉价的氢气为氢源,由潜手性的酮不对称加氢是制备手性醇最好的方法之一[1].但存在手性催化剂的膦配体不稳定以及贵金属(Ru、 Rh)的流失等问题.硼氢化钠是一种较温和的氢化试剂,Mukaiyama等用具有C2对称轴的一系列光学活性的二亚胺钴配合物催化硼氢化钠不对称还原芳香酮,实现了以硼氢化钠为氢源的不对称氢化反应[2].     

手性羰基铁体系催化酮的不对称氢转移氢化

手性羰基铁络合物很少被用于芳香酮的不对称氢转移氢化.利用不同的羰基铁络合物与手性双胺双膦配体现场络合,形成手性胺膦铁催化体系.考察了它们对多种芳香酮的不对称氢转移催化氢化性能.结果表明,三核的手性胺膦铁簇合物是催化芳香酮不对称氢转移氢化的较好体系.当用三核的铁簇合物[Et₃NH]⁺[HFe₃(CO)₁₁]^-体系催化1,1-二苯基丙酮的氢化时,最高可获得98%的对映选择性.通过现场红外光谱测定,揣测羰基铁簇合物Fe₃(CO)₁₂在催化反应过程中保持三核的簇合物的簇骼不变.     

新型手性胺膦-铱体系催化芳香酮的不对称转移氢化

合成了含-CH_3取代基的PNNP型手性双胺双膦配体, 并采用核磁共振、质谱、红外光谱及圆二色光谱等方法对其进行了表征. 在异丙醇溶液中, 考察了该配体与[IrHCI_2(COD)]_2组成的手性胺膦-铱体系对多种芳香酮的不对称转移氢化性能. 结果表明, 该手性胺膦-铱体系是催化多种芳香酮不对称氢转移氢化的优秀催化剂. 在室温下, 用该体系催化1,1-二苯基丙酮时, 可得到99%的转化率和99% ee的对映选择性.     

手性双胺双膦-铱体系催化芳香酮的高对映选择性氢转移氢化

在异丙醇溶液中,从[Ir(COD)Cl]2和C2-对称的手性双胺双膦配体原位制备了手性能-Ir(Ⅰ)配合物,并直接用于催化几种芳香酮的不对称氢转移氢化。结果表明,该配合物是异丙基苯基酮不对称转移氢化的优秀催化剂,当底物酮与催化剂的摩尔比(S/C)为1200:1时,在室温下反应4h后,得到相应的手性芳香醇的转化率和对映选择性分别高达98%和98%ee.     

手性双胺双膦-铱体系催化芳香酮的高对映选择性氢转移氢化

在异丙醇溶液中,从[Ir(COD)Cl]2和C2-对称的手性双胺双膦配体原位制备了手性能-Ir(Ⅰ)配合物,并直接用于催化几种芳香酮的不对称氢转移氢化。结果表明,该配合物是异丙基苯基酮不对称转移氢化的优秀催化剂,当底物酮与催化剂的摩尔比(S/C)为1200:1时,在室温下反应4h后,得到相应的手性芳香醇的转化率和对映选择性分别高达98%和98%ee.     

非贵金属催化酮的不对称硅氢加成反应的研究进展

手性二级醇作为手性药物、香料等的原料,主要通过不对称加氢来制备.近来通过不对称硅氢加成的方法来制备手性醇的方法,由于其温和的反应条件及相对低廉的催化剂成本而受到广泛关注.介绍了近年来锌、铁、铜、钛等非贵金属催化剂催化潜手性酮的不对称硅氢加成反应的研究进展.     

芳香酮的不对称还原*

本文从化学方法和生物方法两个角度,化学催化法、手性试剂法和酶催化法三个方面综述了近年来芳香酮的不对称还原进展。文章概述了芳香酮取代基的电子效应与空间效应、手性催化剂和手性试剂的结构、反应体系等对产物光学活性的影响,以及全细胞酶、分离酶等不同生物催化体系中芳香酮结构对产物光学活性的影响,并展望了不对称还原的研究及应用前景。     

有机催化不对称合成3,4-二氢吡喃-2-酮和3,4-二氢吡啶-2-酮衍生物研究进展

3,4-二氢吡喃-2-酮和3,4-二氢吡啶-2-酮结构广泛存在于多种天然产物和具有药理活性的分子中,因此高效合成手性3,4-二氢吡喃-2酮和3,4-二氢吡啶-2酮受到越来越多药物化学和有机化学研究者的关注.近年来有机小分子催化的不对称反应已成为构建手性杂环化合物的有效方法.综述了自2003年至今有机小分子催化的不对称反应合成手性3,4-二氢吡喃酮和3,4-二氢吡啶酮衍生物的研究进展,并根据不同的催化剂类型及反应机理进行分类讨论.     

手性Salen-Co(Ⅱ)配合物催化芳香酮不对称还原反应研究

目前 ,以廉价的氢气为氢源 ,由潜手性的酮不对称加氢是制备手性醇最好的方法之一 [1] .但存在手性催化剂的膦配体不稳定以及贵金属 ( Ru、Rh)的流失等问题 .硼氢化钠是一种较温和的氢化试剂 ,Mukaiyama等用具有 C2 对称轴的一系列光学活性的二亚胺钴配合物催化硼氢化钠不对称还原芳香酮 ,实现了以硼氢化钠为氢源的不对称氢化反应 [2 ] .手性 Salen是一种用途广泛的配体 ,已用在不对称催化环氧化 [3 ]、环丙烷化 [4]、杂 Diels- Alder反应 [5]及环氧化合物的水解动力学拆分 [6]、仲醇动力学拆分[7] 等反应中 ,并显示出很好的不对称诱导效…     

Highly efficient iridium catalyst for asymmetric transfer hydrogenation of aromatic ketones under base-free conditions

[reaction: see text] Catalytic systems generated in situ from the chiral PNNP ligands with iridium or rhodium hydride complexes exhibited excellent catalytic activity and good enantioselectivity in the asymmetric transfer hydrogenation of aromatic ketones without added base. The best result was obtained in the IrH(CO)(PPh(3))(3)-ligand 2 catalytic system with up to 99% yield and 97% ee.     

新型手性环状胺膦配体的设计合成及在酮的不对称还原中的应用

新型手性配体的设计合成是不对称催化研究的重要内容,其中手性胺膦配体因同时含有"软"的磷原子和"硬"的氮原子而具有丰富的配位化学性能和优秀的不对称诱导能力.本文总结了本研究组最近设计合成的手性环状胺膦配体的制备、表征及其在铁催化酮的不对称还原中的应用.手性1,2-环己二胺与双(2-甲酰基苯基)苯基膦通过[2+2]环缩合反应能够顺利获得手性22元环的亚胺膦配体21,该配体经Na BH4还原后生成大环胺膦配体22.利用手性大环胺膦配体22与Fe3(CO)12原位生成的催化体系,能够高活性、高对映选择性地实现包括杂环芳香酮在内50多种酮的不对称转移氢化和不对称氢化反应,其S/C(底物与催化剂的摩尔比)最高可达5000:1,产物手性芳香醇的光学纯度高达99%ee.     

Magnetically recoverable SiO2-coated Fe3O4 nanoparticles: a new platform for asymmetric transfer hydrogenation of aromatic ketones in aqueous medium

A magnetically recoverable chiral rhodium catalyst exhibited excellent catalytic activity and enantioselectivity in asymmetric transfer hydrogenation of aromatic ketones in aqueous medium, which could be recovered easily via a small magnet and used repetitively ten times without obviously affecting its enantioselectivity.     

Recoverable organorhodium-functionalized polyhedral oligomeric silsesquioxane: a bifunctional heterogeneous catalyst for asymmetric transfer hydrogenation of aromatic ketones in aqueous medium

A bifuctional heterogeneous chiral rhodium catalyst exhibited excellent catalytic activity and enantioselectivity in asymmetric transfer hydrogenation of aromatic ketones and their analogues in aqueous medium, which could be recovered easily and used repetitively without affecting obviously its enantioselectivity.     

Design of novel polymer-supported chiral catalyst for asymmetric transfer hydrogenation in water

New polymer-supported chiral sulfonamides containing sulfonated pendant group have been synthesized. Chiral catalyst prepared from the new polymer-support is more effective for asymmetric transfer hydrogenation of aromatic ketones in water compared to that prepared from conventional polystyrene-support. Polymer-supported catalysts containing quaternary ammonium salt as a pendant increased not only the reactivity but also the enantioselectivity in asymmetric transfer hydrogenation in water. Moreover, this type of polymer can be reused without loss of the catalytic activity.     

Novel chiral multidentate P3N4-type ligand for asymmetric transfer hydrogenation of aromatic ketones

Novel chiral multidentate P₃N₄-type ligand has been synthesized and characterized by NMR and HRMS. Using i-PrOH as solvent and hydrogen source, asymmetric transfer hydrogenation of various ketones was investigated. The catalyst generated in situ from chiral multidentate aminophosphine ligand (R,R,R,R)-3 and IrCl(CO)(PPh₃)₂ exhibited highly catalytic activity and excellent enantioselectivity under mild conditions, achieving the corresponding chiral alcohols with up to 99% yield and 99% ee.     

Asymmetric transfer hydrogenation catalysed by hydrophobic dendritic DACH-rhodium complex in water

Hydrophobic Fréchet-type dendritic chiral 1,2-diaminocyclohexane-Rh(III) complexes have been applied in the asymmetric transfer hydrogenation of ketones in water using HCOONa as hydrogen source. The catalysts were found to be finely dissolved in the liquid substrates in the aqueous mixture and exhibited high catalytic activity and enantioselectivity (52-97% ee). The catalytic loading could be decreased to 0.01 mol% and good conversion was still obtained with excellent enantioselectivity. Moreover, the catalyst could be easily precipitated from the mixture by adding hexane and reused several times without affecting the high enantioselectivity.     

Achiral benzophenone ligand-rhodium complex with chiral diamine activator for high enantiocontrol in asymmetric transfer hydrogenation

The chirality of an achiral benzophenone-based rhodium complex can be controlled by chiral diamines to afford significantly high enantioselectivity in the catalytic asymmetric transfer hydrogenation of ketones (up to 99% ee, 99% yield).