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％．     

羊毛-钯配合物催化反式-2-丁烯酸的不对称水合反应 Efficient Asymmetric Hydration of trans-2-Butenoic Acid Catalyzed by Wool-Palladium Complex

 羊毛-钯配合物作为一种生物高分子金属催化剂制备简单,性能稳定,具有很高的立体选择性. 它能有效地催化反式-2-丁烯酸水合,得到手性化合物(S)-(+)-β-羟基丁酸,其产率和光学收率分别为88.4%和93.0%. 钯的负载量、底物/催化剂比、反应温度和反应时间对产物产率和光学收率有很大的影响. 催化剂重复使用多次后,产物产率和光学收率没有明显变化.     

聚合物负载的手性联二萘酚的合成及其在不对称催化中的应用进展

作为一种有机配体, 手性1,1'-联二萘酚(BINOL)被广泛应用于过渡金属催化的均相不对称有机反应. 为克服均相催化剂不易回收重复使用等缺陷, 人们深入研究了聚合物负载手性BINOL催化剂的方法. 总结了近年来聚合物负载手性BINOL催化剂的合成及其在不对称有机催化中的应用, 并对负载型BINOL催化剂进行了展望.     

水相中交联型聚合物负载的Pd催化氨基醇氧化羰化反应

在水相无助剂条件下,将含有离子液基团的聚合物负载的Pd催化剂用于催化氨基醇氧化羰化反应高效合成噁唑烷酮.催化剂能够重复使用5次而活性没有明显降低.     

负载型CaSO4/离子交换树脂催化合成单十二烷基磷酸酯

采用浸渍法制备了负载型金属盐离子交换树脂催化剂,考察了以磷酸与月桂醇为原料催化合成单十二烷基磷酸酯的催化性能.负载不同金属盐离子对单十二烷基磷酸酯的收率的影响表明,CaSO4负载离子交换树脂催化合成单十二烷基磷酸酯效果最好.研究发现,在CaSO4负载量1.2%,催化剂用量为总反应物质量的3%,反应温度90℃,反应12h工艺条件下,月桂醇的转化率为79.4%,单酯选择性为99.9%;加入环己烷作为带水剂,相同条件下,月桂醇转化率为92.3%,单酯选择性为99.9%,并且催化剂重复使用7次之后,催化性能仍保持不变.     

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％。     

新型手性氢化喹啉唑啉配体的合成

以8-喹啉羧酸为原料,通过8-喹啉酰氯与手性氨基醇反应或8-喹啉羧酸乙酯与氨基醇的酯交换反应制得酰胺6a-c,再经Ni-Al合金催化还原、甲磺酸催化脱水关环,合成了新型手性氢化喹啉唑啉配体2a-c.在苯乙酮的不对称催化氢转移反应的初步研究中,使用2C与RuCl2(Cymene)]2形成的手性催化剂得到71%产率和44%的e.e值.     

改性活性炭负载三聚磷酸二氢铝催化合成苯甲醛乙二醇缩醛

采用硝酸改性活性炭后负载三聚磷二氢铝用于催化合成苯甲醛乙二醇缩醛,通过单因素实验考察醇醛摩尔比、催化剂用量及反应时间等因素对产品收率的影响,并采用正交实验获取较佳工艺条件。 结果表明,该催化反应中,当反应温度为110 ℃时,各因素对收率的影响顺序为:醇醛比>反应时间>带水剂加入量>催化剂用量。 优化反应条件为:苯甲醛0.2 mol,醇醛摩尔比2.5,反应时间75 min,催化剂加入量4%(占反应物总质量),带水剂加入量25 mL,苯甲醛乙二醇缩醛收率86.5%,催化剂经5次重复使用后收率仍大于86.0%。     

新型有机小分子催化剂的合成及其在α-酮亚胺基酯的不对称氢化硅烷化反应中的应用

杂环芳香酸和手性氨基醇通过缩合反应制备了9个新型手性有机小分子催化剂(3a～3i),其结构经1H NMR, 13C NMR和MS表征.3用于催化α-酮亚胺基酯的不对称氢化硅烷化反应(三氯硅烷为还原剂),可得到高收率和中等对映选择性的手性α-氨基酸酯.     

含光学活性联二萘酚基团可溶性高分子手性配体的合成及其不对称加成反应

不对称催化是有机化学研究的前沿领域和发展方向．近10年来，手性配体的研究得到了长足的发展，大量的小分子手性配体被报道，其中许多手性配体展示了优异的催化性能．但是由于昂贵的手性配体（金属催化剂）分离、回收和再利用的问题，从而限制了小分子催化剂的应用．因此，解决手性金属催化剂的分离与回收问题是不对称催化研究领域的一个热点问题．为了解决这一关键问题，国内外科学家从负载的角度出发已经成功地发展了众多的研究方法，无机负载法、交联高分子负载法、可溶性高分子负载法、树状大分子负载法等．许多负载的手性金属催化剂已经表现出优异的催化活性和高的对映选择活性．     

Novel polymer-supported chiral catalysts for the asymmetric addition of diethylzinc to aldehydes

Newly synthesized polymer-supported chiral amino alcohol catalysts 5a and 5b have been proved to be effective for the enantioselective addition of diethylzinc to aldehydes, affording the corresponding sec-alcohols in moderate enantiomeric excesses with good to excellent yields. The recycled catalyst could be reused in the same reaction without significant deterioration in performance.     

聚甲基丙烯酸羟乙酯负载手性Mn(III)salen配合物催化α-甲基苯乙烯的不对称环氧化反应(英文)

在手性Mn(III)salenCl配合物的5和5'位上引入氨基醇,将其通过轴配位作用负载于聚甲基丙烯酸羟乙酯(pHEMA)上,并用于离子液体[bmim]PF6中,催化α-甲基苯乙烯的不对称环氧化反应.结果表明,该催化剂表现出良好的催化活性和区域选择性,对映体过量值(ee)和产率可分别达80%～91%和84%～92%,循环使用5次后催化活性没有明显降低.这可归结为氨基醇和环己二胺中手性碳原子间相互协同作用.     

Nickel‐Catalyzed Asymmetric Hydrogenation of 2‐Amidoacrylates

Earth‐abundant nickel, coordinated with a suitable chiral bisphosphine ligand, was found to be an efficient catalyst for the asymmetric hydrogenation of 2‐amidoacrylates, affording the chiral α‐amino acid esters in quantitative yields and excellent enantioselectivity (up to 96 % ee). The active catalyst component was studied by NMR and HRMS, which helped us to realize high catalytic efficiency on a gram scale with a low catalyst loading (S/C=2000). The hydrogenated products could be simply converted into chiral α‐amino acids, β‐amino alcohols, and their bioactive derivatives. Furthermore, the catalytic mechanism was investigated using deuterium‐labeling experiments and computational calculations.     

Enantioselective decarboxylation of beta-keto esters with Pd/amino alcohol systems: successive metal catalysis and organocatalysis

The kinetics and mechanisms of one-pot cascade reactions of racemic beta-keto esters to give chiral ketones in the presence of Pd/C-chiral amino alcohol catalyst systems were studied. Transformation of 2-methyl-1-tetralone-2-carboxylic acid benzyl ester (1) into 2-methyl-1-tetralone (4) in the presence of Pd/C and cinchona alkaloids or ephedrine was chosen as a model reaction. After the first reaction step, the Pd-catalysed debenzylation of 1 to afford the corresponding beta-keto acid (2), there are two possible reaction routes that may be catalysed by the chiral amino alcohol in solution or by Pd(0) sites on the metal surface in cooperation with the adsorbed amino alcohol. The reaction intermediate 2 was synthesized, and the kinetics of decarboxylation were followed by NMR, UV and IR spectroscopy. The studies revealed that the role of Pd is to trigger the reaction series by deprotection of 1. The subsequent dominant reaction route from the racemic beta-keto acid 2 to the chiral ketone 4 is catalysed by the chiral amino alcohol in the liquid phase. It is shown that kinetic resolution of the diastereomeric salt of rac-2 and the chiral amino alcohol plays a key role in the enantioselection. High enantioselectivity necessitates an amino alcohol/rac-2 ratio of at least 2. A high ratio favours the formation of 1:1 amino alcohol/acid diastereomeric complexes, and the second amino alcohol molecule may be responsible for the enantioselective protonation of 2 in the diastereomeric complex.     

N-磺化手性β-氨基醇修饰的钛试剂催化下的酮的不对称炔基化反应研究

The easily prepared and recoverable chiral N-sulfonylated fl-amino alcohol 2 in combination with Ti（OPr-i）4 was found to be an effective chiral catalyst for the enantioselective addition of alkynylzinc to ketones, which gave the useful products, i.e. chiral tertiary propargyl alcohols, with the ee up to 92%.     

Asymmetric diethyl- and diphenylzinc additions to aldehydes by using a fluorine-containing chiral amino alcohol: a striking temperature effect on the enantioselectivity, a minimal amino alcohol loading, and an efficient recycling of the amino alcohol

A chiral pyrrolidinylmethanol derivative containing perfluoro-ponytails (5) was prepared from (S)-proline. The use of this perfluoro-substituted amino alcohol in catalytic asymmetric additions of organozinc reagents to aldehydes affords products with high enantioselectivities in both pure hexane and a mixture of hexane and FC-72 (perfluorohexane). Enantiomeric excesses up to 94 and 88 % ee have been achieved in Et(2)Zn and Ph(2)Zn additions, respectively. For the reactions in the biphasic solvent system a striking temperature effect was observed. Thus, when the temperature was raised from 0 to 40 degrees C the ee value of the product increased from 81 to 92 %. Furthermore, the catalyst loading could be remarkably low, and with only 0.1 mol % of amino alcohol 5 a product with 90 % ee was obtained in the Et(2)Zn addition to benzaldehyde in hexane. The perfluoro-ligand was easily recovered by simple phase separation, and until the ninth repetition its reuse proceeded without significant loss of enantioselectivity and reactivity.     

A highly enantioselective Diels-Alder reaction of 1,2-dihydropyridine using a simple β-amino alcohol organocatalyst for a practical synthetic methodology of oseltamivir intermediate

An easily prepared chiral amino alcohol catalyst was found to provide an efficient synthetic intermediate of oseltamivir with excellent chemical yield and enantioselectivity (up to 98% yield and up to 98% ee) in enantioselective Diels-Alder reactions of 1,2-dihydropylidines with acroleins.     

聚乙二醇(400)中的不对称Baylis-Hillman反应

从易得的L-脯氨酸出发, 方便地合成了氨基醇1. 以聚乙二醇(400)为溶剂, 考察了手性氨基醇1 (30 mol%)在聚乙二醇(400)中催化不对称的Baylis-Hillman反应, 有较好的催化活性和立体选择性, 产率最高达95.4%, ee值最高达54.3%. 手性氨基醇1-聚乙二醇(400)催化体系可方便回收并重复利用, 在前三次循环中, 未发现反应产率和选择性有明显变化.     

新型（Salen）Co催化剂催化合成沙丁胺醇

以（Salen）Co-GaC13为催化剂,拆分2-乙酰氧基5-环氧乙基-乙酸苄酯以得到R-型产品,设计新的手性沙丁胺醇的合成路线.结果表明,以（Salen）Co-GaCl3为催化剂、异丙醇为溶剂、水为亲核试剂,拆分2-乙酰氧基-5-环氧乙基-乙酸苄酯所得的产品光学纯度达到97.36％ ee.该方法催化剂廉价易得,拆分过程简便、成本低廉,具备工业化生产的潜力.     

不对称反应的对映体过量值预测

建立了手性催化剂结构与反应产物对映体过量值的定量结构-活性相关性模型, 以辅助苯乙酮不对称氢转移反应的催化剂筛选. 手性催化剂由手性氨醇配体与金属络合物合成, 故采用构象独立手性指数或构象依赖手性指数描述手性氨醇配体, 采用指示变量区分金属络合物, 然后合并2个指数来描述手性催化剂. 通过遗传算法进行变量选择, 采用随机森林法建立数学模型以预测对映体过量值, 测试集的相关系数R²=0.769, 整个数据集的OOB(Out-of-bag)交叉验证结果为R²=0.785.