新型手性氨基醇的合成及其用于不对称催化醛类烷基化反应

制备了一种由糖类化合物衍生的新型手性氨基醇（Ⅰ），并将其作为手性源用于醛类的不对称烷基化反应．考察了在手性氨基醇的存在下，各种醛和二乙基锌作用生成相应的手性仲醇的光学收率及化学收率．结果表明，该催化剂对于芳香醛的烷基化更为有效．并考察了几种反应条件对于苯甲醛的不对称催化烷基化反应的影响，其中最佳结果为１－苯基－１－丙醇的光学收率达８２．７％，而化学收率达５８．８％．     

新型手性β—氨基醇用于不对称催化醛类烷基化反应

将自己研制的一种新型β－氨基醇作为手性源用于醛类的不对称催化烷基化反应。考察了在这种手性β－氨基醇存在时各种醛和二乙基锌作用生成相应的手性仲醇的光学收率，考察了几种反应条件参数对于苯甲醛的这种不对称催化反应的影响，其中最佳结果为１－苯基丙醇的光学收率达７４．１％，而其化学产率达９３．８％。     

新型手性基醇的合成及其用于不对称催化醛类烷基化反应

制备了一种由糖类化合物衍生物新型手性氨基醇（Ｉ），并将其作为手性源用于醛类的不对称烷基化反应，考察了在手性氨基酸的存在下，各种醛和二乙基锌作用生成相应的手性仲醇的光学收率及化学收率，结果表明，该催化剂地于芳香醛的烷基化更为有效，并考察了几种反应条件对于苯甲醛的不对称催化烷基化反应的影响，其中最佳结果为１－苯基－１－两醇的光学收率达８２．７％，而化学收率达５８．８％。     

新型手性β－氨基醇用于不对称催化醛类烷基化反应

将自己研制的一种新型β－氨基醇（Ⅰ）作为手性源用于醛类的不对称催化烷基化反应。考察了在这种手性β－氨基醇（催化量）存在时各种醛和二乙基锌作用生成相应的手性仲醇的光学收率。考察了几种反应条件参数对于苯甲醛的这种不对称催化反应的影响，其中最佳结果为１－苯基丙醇的光学收率达７４．１％，而其化学产率达９３．８％。     

吡咯烷类手性二胺配体N-烷基化物的简易合成法

吡咯烷类及有关的手性二胺配体通过使用氯化锌-多聚甲醛-硼氢化钾或硼氢化钠一锅煮反应进行烷基化,具有产率高、操作简易等优点。     

两种手性β-氨基醇的合成

以（Ｓ）－脯氨酸为原料,经３步反应合成（Ｓ）－２－（二苯基羟甲基）－四氢吡咯;以羟脯氨酸为原料,经４步反应合成（２Ｓ,４Ｓ）－２－（二苯基羟甲基）－４－苯氧基－四氢吡咯。     

吡咯烷类手性二胺配体N-烷基化物的简易合成法(英文)

吡咯烷类及有关的手性二胺配体通过使用氯化锌-多聚甲醛-硼氢化钾或硼氢化钠一锅煮反应进行烷基化,具有产率高、操作简易等优点。     

基于D-葡糖胺的手性β-氨基醇的合成

手性氨基醇作为催化剂广泛应用于多种不对称合成反应中。以D-葡糖胺为原料设计合成一系列新型手性β-氨基醇。D-葡糖胺首先与氯甲酸甲酯缩合,再先后经过甲基化、苄叉保护、碱性水解反应,得4,6-O-苄叉基-2-脱氧-2-氨基-α-D-吡喃葡萄糖甲苷,进一步将其通过N-烃化反应或N-磺酰化反应合成得手性β-氨基醇。产物结构经1H NMR,13C NMR和MS表征确证。     

Trifluoromethylated amino alcohols as chiral ligands for highly enantioselective Reformatsky reaction

The enantioselective Reformatsky reaction of PhCHO was achieved by the use of trifluoromethylated amino alcohols as chiral ligands to afford the corresponding optically active β-hydroxy ester with up to 90% ee.     

新型多齿手性氨基醇的合成和结构表征

以L-苯甘氨酸和N,N-二甲基苯胺为原料,合成了2种新型多齿手性氨基醇S-1,1,2-三苯基-2-[(2-二甲氨基-5-溴-1-苯基)甲氨基]-1-乙醇和S-2-苯基-2-[(2-二甲氨基-5-溴-1-苯基)甲氨基]-1-乙醇;利用红外光谱仪、核磁共振谱仪及质谱仪表征了合成产物的结构.     

Synthesis and metal complexes of chiral c(2)-symmetric diamino-bisoxazoline ligands

A synthetic route to tetradentate chiral N(4) ligands has been developed with the aim to study the potential of corresponding iron and manganese complexes as catalysts for enantioselective epoxidation. These ligands, which contain two oxazoline rings and two trialkylamino groups as coordinating units, are readily prepared in enantiomerically pure form by the reaction of chiral 2-chloromethyloxazolines with achiral N,N'-dimethylethane-1,2-diamine or chiral (R,R)-N,N'-dimethylcyclohexane-1,2-diamine. The ligands derived from N,N'-dimethylethane-1,2-diamine reacted with anhydrous metal halides MnCl(2) and FeCl(2) in a stereoselective manner to give octahedral mononuclear complexes that have the general formula Delta-[(L)MCl(2)]. In contrast, the ligands derived from N,N'-dimethylcyclohexane-1,2-diamine formed complexes with different coordination modes depending on the diastereomer employed: in one case the metal ion was found to be pentacoordinate, in the other case a hexacoordinated complex was observed. The structure of a series of Fe and Mn complexes was determined by X-ray analysis. The coordination chemistry of these ligands was further studied by X-ray and NMR analyses of the diamagnetic isostructural complexes [(L)ZnCl(2)]. Analogous ionic complexes, which were prepared by removing chloride with silver trifluoromethanesulfonate or hexafluoroantimonate, were tested as catalysts for the epoxidation of olefins.     

手性氨基醇在不对称催化中的应用及新进展

综述了手性氨基醇作为配体或催化剂在不对称合成中的应用及最新进展。     

Enantioselective addition of diethylzinc to aldehydes catalyzed by β‐amino alcohols derived from (1R,2S)‐norephedrine

β‐Amino alcohols derived from (1R,2S)‐norephedrine were synthesized and used as ligands in the catalytic enantioselective diethylzinc addition to benzaldehydes. N‐alkylated (1R,2S)‐norephedrine‐based derivative 3a gave the highest enantioselectivity. The effects of different parameters on the enantioselectivity of the product were investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

Efficient asymmetric addition of diethylzinc to aldehydes using C2‐novel chiral pyridine β‐amino alcohols as chiral ligands

A series of novel C₂‐symmetric chiral pyridine β‐amino alcohol ligands have been synthesized from 2,6‐pyridine dicarboxaldehyde, m‐phthalaldehyde and chiral β‐amino alcohols through a two‐step reaction. All their structures were characterized by ¹H NMR, ¹³C NMR and IR. Their enantioselective induction behaviors were examined under different conditions such as the structure of the ligands, reaction temperature, solvent, reaction time and catalytic amount. The results show that the corresponding chiral secondary alcohols can be obtained with high yields and moderate to good enantiomeric excess. The best result, up to 89% ee, was obtained when the ligand 3c (2S,2′R)‐2,2′‐((pyridine‐2,6‐diylbis(methylene))bisazanediyl))bis(4‐methyl‐1,1‐diphenylpentan‐1‐ol) was used in toluene at room temperature. The ligand 3g (2S,2′R)‐2,2′‐((1,3‐phenylenebis(methylene))bis(azanediyl))bis(4‐methyl‐1,1‐diphenylpentan‐1‐ol) was prepared in which the pyridine ring was replaced by the benzene ring compared to 3c in order to illustrate the unique role of the N atom in the pyridine ring in the inductive reaction. The results indicate that the coordination of the N atom of the pyridine ring is essential in the asymmetric induction reaction. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and Crystal Structure of (2S,2'S,4'R)-2-(1-Hydroxy-1-ethylpropyl)-1-[(1'-p-tosyl-4'-hydroxypyrrolidin-2'-yl)methyl]pyrrolidine

1 INTRODUCTION In recent years, chiral β-amino alcohols have attracted much attention due to their special bio- logical functions and catalytic activities. Chiral β- amino alcohol moieties are usually found not only in natural products (e.g., cinchona alkaloids, ephe- drine, toxal, etc.) with special biological activities[1, 2], but also critical structural segments of some syn- thesized biologically active compounds, such as adrenergic agonists or antagolist[3, 4] and inhibitors for HI…     

Racemization of chiral amino alcohols: Catalyst selection and characterization

Summary The transformation of R-(-)-2-amino-1-butanol to the racemic mixtures was selected as a model for the racemization of chiral amino alcohols. A 40% Co/γ-Al2O3 catalyst was found to be active enough for the complete racemization in over 80% yield and characterized by XRD, XPS, TPR and BET, etc.     

手性氨基醇（R）－2－氨基－1，1－二苯基－3－（2－萘基）－1－丙醇：制备及其对前手性酮硼烷还原的对映选择性催化作用

用丙二酸酯法合成了Ｎ－乙酰基－３－（２－萘基）－ＤＬ－α－丙氨酸乙酯３．３经酶法拆分，得光学活性的Ｄ－３，后者经盐酸水解、酯化后再与苯基溴化镁作用，制得标题化合物６。在０．５ｍｍｏｌ６存在下，用过量硼烷对一系列前手性酮还原，得到了相应的光学活性二级醇。对映体过量（ｅ．ｅ值）５７．０～１００％。     

Atropisomeric discrimination in new Ru(II) complexes containing the C(2)-symmetric didentate chiral phenyl-1,2-bisoxazolinic ligand

A new family of Ru(II) complexes containing the tridentate meridional 2,2':6',2'-terpyridine (trpy) ligand, a C(2)-symmetric didentate chiral oxazolinic ligand 1,2-bis[4'-alkyl-4',5'-dihydro-2'-oxazolyl]benzene (Phbox-R, R = Et or iPr), and a monodentate ligand, of general formula [Ru(Y)(trpy)(Phbox-R)](n+) (Y = Cl, H(2)O, py, MeCN, or 2-OH-py (2-hydroxypyridine)) have been prepared and thoroughly characterized. In the solid state the complexes have been characterized by IR spectroscopy and by X-ray diffraction analysis in two cases. In solution, UV/Vis, cyclic voltammetry (CV), and one-dimensional (1D) and two-dimensional (2D) NMR spectroscopy techniques have been used. We have also performed density functional theory (DFT) calculations with these complexes to interpret and complement experimental results. The oxazolinic ligand Phbox-R exhibits free rotation along the phenyloxazoline axes. Upon coordination this rotation is restricted by an energy barrier of 26.0 kcal mol(-1) for the case of [Ru(trpy)(Phbox-iPr)(MeCN)](2+) thus preventing its potential interconversion. Furthermore due to steric effects the two atropisomers differ in energy by 5.7 kcal mol(-1) and as a consequence only one of them is obtained in the synthesis. Subtle but important structural effects occur upon changing the monodentate ligands that are detected by NMR spectroscopy in solution and interpreted by using their calculated DFT structures.