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1.
光学活性芳基醇化合物是一类重要的手性砌块,可用于合成多种手性药物,其制备技术研究是近年来的研究热点。与传统的化学制备方法相比,生物催化方法由于具有选择性高、反应条件温和以及环境危害少等优点更具吸引力。通过生物催化不对称还原芳基酮是合成对映体纯芳基醇最有效的方法之一。本文综述了生物催化不对称还原制备手性芳基醇的研究进展,重点介绍了不同形式的生物催化剂应用于生物不对称还原的研究现状,包括微生物细胞、酶、重组工程菌以及固定化细胞等,概述了有机溶剂、表面活性剂和离子液体等底物助溶剂对生物不对称催化的影响,并对生物催化制备对映体纯芳基醇的研究前景进行了展望。  相似文献   

2.
王强  顾庆  游书力 《化学学报》2019,77(8):690-704
在手性分子中,轴手性化合物占据着非常重要的地位.从原子和步骤经济性方面考虑,利用不对称碳-氢官能团化反应构建轴手性化合物是最简洁高效的方法.随着过渡金属催化的不对称碳-氢键官能团化领域的逐步发展,利用该策略来构建轴手性联芳基化合物的研究成果也不断涌现.本文综述了通过过渡金属钯、铑和铱催化的不对称碳-氢键官能团化反应合成轴手性联芳基化合物的最新进展.此外,还介绍了利用这些方法合成多种轴手性配体及其催化的不对称反应,以及这些方法在天然产物合成中的应用.  相似文献   

3.
手性环氧化物在合成上具有重要的应用价值。近年来,制取这些手性合成物的合成方法取得了很大的发展。文章重点讨论了生物催化手性前体烯烃不对称合成光学活性环氧化合物的发展状况。  相似文献   

4.
含氮配位基团的二茂铁衍生物的环钯化合物在有机合成、催化等领或有着重要的应用,尽管目前已经合成了从多的二茂铁环钯化合物,但其中绝大部分为外消旋体。二茂铁是引入平面手性的理想骨架,通过经典的拆分方法或利用光学纯的二茂铁配体进行不对称环钯化反应可得到具有平面手性的二茂铁环钯化合物,研究发现,利用平面手性的二茂铁环钯化合物与金属汞嘲、锡等的金属转移反应可方便地制备平面构型保持的手性环汞、环锡化合物;还可将它们用于外消旋氨基酸的手性拆分及催化不对称Claisen重排反应(ee值最高可达95%)。  相似文献   

5.
杨尧  文俊杰  吴广文 《化学通报》2022,85(5):566-574
手性炔丙醇是一种重要中间体化合物,作为合成多种光学活性化合物的重要合成前体受到学者们广泛关注。目前通过酮的不对称催化反应合成手性炔丙醇的研究开发具有极大发展前景,因此本文围绕酮类化合物的不对称催化反应来进行综述,结合相关反应最新研究进展,全面总结并分类了不对称催化还原、催化不对称加成等反应类型,介绍了合成不同结构手性炔丙醇的新思路,并对酮的不对称催化反应在未来能成为工业化重要生产途径作出展望。  相似文献   

6.
张文虎  蔡燕  刘湘  方云  许建和 《化学进展》2007,19(10):1537-1553
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。  相似文献   

7.
在不对称催化反应中,平面手性二茂铁化合物是一类非常高效的手性配体和催化剂.从原子和步骤经济性方面考虑,与传统方法相比不对称碳氢键直接官能团化反应是构建平面手性二茂铁最简洁有效的方法.综述了铜、钯、铑、铱、金和铂等过渡金属催化的不对称碳氢键官能团化反应合成平面手性二茂铁化合物的最新进展.此外,还介绍了利用这些方法合成多种平面手性二茂铁配体和催化剂及其不对称催化反应.  相似文献   

8.
王文芳 《有机化学》2023,(9):3146-3166
过渡金属催化不对称C—H硼化反应是构建手性有机硼化合物最为有效的策略之一,具有原子和步骤经济性,在合成化学、药物化学和材料学等领域受到广泛关注.新型手性配体的设计与合成是过渡金属催化不对称C—H硼化反应成功的关键,根据手性配体的设计和发展过程,对近年来实现的过渡金属催化不对称C(sp2)—H和C(sp3)—H硼化反应的研究进展进行综述.  相似文献   

9.
面包酵母在催化不对称合成中的应用   总被引:8,自引:0,他引:8  
介绍了当前国内外在以面包酵母为催化剂不对称催化合成手性化合物的研究情况,重点介绍了面包酵母催化各类潜手性羰基的不对称还原、潜手性碳一碳双键的不对称加成和碳一碳键形成的反应情况,讨论了各种提高酵母催化不对称合成反应立体选择性的方法,对酵母催化不对称合成有关生物学方面的研究进行了简单的介绍。  相似文献   

10.
何青  万南微  陈永正 《合成化学》2018,26(3):214-228
C-H键的不对称羟基化反应是有机合成领域的研究热点和难点之一。生物催化的不对称羟基化反应具有较好的区域选择性和立体选择性,可作为化学催化C-H键不对称羟基化方法的有力补充,而目前关于生物催化的C-H键不对称羟基化反应的评论文章鲜有报道。本文结合本课题组的研究基础,根据底物类型,综述了生物催化链烷烃、环烷烃、芳香烷烃、烯烃、杂环化合物和天然化合物的不对称羟基化反应的进展,参考文献44篇。  相似文献   

11.
B. Baskar  N.G. Pandian  K. Priya  Anju Chadha   《Tetrahedron》2005,61(52):12296-12306
Candida parapsilosis ATCC 7330 was found to be an efficient biocatalyst for the deracemisation of aryl α-hydroxy esters (65–85% yield and 90–99% ee). A variety of aryl and aryl substituted α-hydroxy esters were synthesized to reflect steric and electronic effects on biocatalytic deracemisation. The mechanism of this biocatalytic deracemisation was found to be stereoinversion.  相似文献   

12.
Deracemisation of racemic or scalemic conglomerates of intrinsically chiral compounds appears to be a promising method of chiral resolution. By combining the established methods of asymmetric synthesis and the physical process of crystal growth, we were able to achieve a complete deracemisation (with 100 % ee) of an asymmetric Mannich product conglomerate—vigorously stirred in its saturated solution—from a starting enantiomeric excess value of 15.8 % in the presence of pyrrolidine (8 mol %) as an achiral catalyst for the CC bond‐forming reaction. Strong activation of this deracemisation process was observed on mild isothermal heating to only 40 °C, resulting in dramatic acceleration by a factor of about 20 with respect to the results obtained at room temperature. Despite the fact that the racemisation half‐life time of the nearly enantiopure Mannich product (with 99 % ee) in the homogenous solution at the reaction temperature is eight days, the deracemisation process took only hours in a small‐scale experiment. This apparent paradox is explained by a proposed rapid enantiomerisation at the crystal/solution interface, which was corroborated by a 13C labelling experiment that confirmed the involvement of rapid enantiomerisation. Frequent monitoring of the solution‐phase ee of the slowly racemising compound further revealed that the minor enantiomer dominated in solution, supporting an explanation based on a kinetic model. A generalisation of the process of “aymmetric autocatalysis” (resulting in automultiplication of chiral products in homogenous media) to encompass heterogeneous systems is also suggested.  相似文献   

13.
《Tetrahedron: Asymmetry》2014,25(12):865-922
This review discusses methods for the metallo-, organo- and biocatalytic asymmetric synthesis of chiral organophosphorus compounds with many applications in stereoselective synthesis with references to updated literature reports as well as the author’s original research. Asymmetric catalytic hydrogenation and reduction with chiral organometallic complexes, together with actively used asymmetric organocatalytic versions of various reactions enable us to synthesize chiral organophosphonates and phosphinates with high enantioselectivity and purity. Asymmetric catalysis is also an effective tool to realize some classic reactions of phosphorus chemistry in a stereospecific manner.  相似文献   

14.
Characteristic features and modern trends in the biocatalytic synthesis of chiral compounds have been discussed. New processes of biocatalytic synthesis use at least two enzymes. Whole cells of recombinant strains are utilized as biocatalysts, and the complete set of target enzymes can be expressed in a single cell.  相似文献   

15.
Directed evolution has been employed to generate new enzymes for the deracemisation of chiral amines.  相似文献   

16.
It has been known for many decades that chiral compounds can be obtained by stereospecific biocatalytic reduction. Further significant methodological developments in this field have, however, only been made during the past ten years; they include the application of previously unused microorganisms and electron donors, the discovery of additional substrates for the known reductases, the development of methods for regenerating reduced pyridine nucleotides, and the discovery of new reductases which were sought for specific preparative purposes. Many chiral compounds can now be synthesized by microbial hydrogenation using H2 and hydrogenase-containing microorganisms as well as by electromicrobial or electroenzymatic reduction. In the two latter methods, anaerobic or aerobic organisms are supplied with electrons from electrochemically reduced, artificial mediators, e.g., methyl viologen. Reductases that do not require pyridine nucleotides and can accept electrons directly from reduced viologens are especially useful. Two examples of this type of enzyme are described which are of preparative interest. Many cells contain methyl viologen-dependent NAD(P) reductases, a large number of which have still not been characterized. A productivity number is proposed which allows different methods of bioconversion with microorganisms to be compared. The productivity numbers of compounds synthesized by the methods described in this review are often 10- to 100-fold higher than those of substances obtained by conventional techniques.  相似文献   

17.
手性是自然界的基本属性之一,不同的手性单体具有不同的生理活性,将手性化合物有效的分离具有十分重要的意义.色谱法和膜分离法在拆分手性化合物中得到了越来越广泛的应用,也是我们课题组采用的主要方法.就近几年来拆分手性化合物的一些方法和研究成果本文进行综述,并对今后手性拆分技术的发展方向进行了展望.  相似文献   

18.
马大友 《化学进展》2008,20(11):1687-1693
手性β-羟基酸及其衍生物是应用化工和有机合成的关键中间体, 生物催化的不对称合成方法以其绿色环保, 简洁高效及高立体选择性已然成为一个新兴的研究热点。本文较系统的总结了生物催化的β-羟基酸及其衍生物不对称合成研究工作,重点介绍了脂肪酶,腈代谢酶及还原酶在合成手性β-羟基酸衍生物中的应用。最后,对今后生物催化不对称合成β-羟基酸的发展方向做一展望。  相似文献   

19.
The scope for biocatalytic modification of non-native carvone derivatives for speciality intermediates has hitherto been limited. Additionally, caprolactones are important feedstocks with diverse applications in the polymer industry and new non-native terpenone-derived biocatalytic caprolactone syntheses are thus of potential value for industrial biocatalytic materials applications. Biocatalytic reduction of synthetic analogues of R-(−)-carvone with additional substituents at C3 or C6, or both C3 and C6, using three types of OYEs (OYE2, PETNR and OYE3) shows significant impact of both regio-substitution and the substrate diastereomer. Bioreduction of (−)-carvone derivatives substituted with a Me and/or OH group at C6 is highly dependent on the diastereomer of the substrate. Derivatives bearing C6 substituents larger than methyl moieties are not substrates. Computer docking studies of PETNR with both (6S)-Me and (6R)-Me substituted (−)-carvone provides a model consistent with the outcomes of bioconversion. The products of bioreduction were efficiently biotransformed by the Baeyer–Villiger monooxygenase (BVase) CHMO_Phi1 to afford novel trisubstituted lactones with complete regioselectivity to provide a new biocatalytic entry to these chiral caprolactones. This provides both new non-native polymerization feedstock chemicals, but also with enhanced efficiency and selectivity over native (+)-dihydrocarvone Baeyer–Villigerase expansion. Optimum enzymatic reactions were scaled up to 60–100 mg, demonstrating the utility for preparative biocatalytic synthesis of both new synthetic scaffold-modified dihydrocarvones and efficient biocatalytic entry to new chiral caprolactones, which are potential single-isomer chiral polymer feedstocks.  相似文献   

20.
A bacterial flavin-containing monooxygenase (FMO), fused to phosphite dehydrogenase, has been used to explore its biocatalytic potential. The bifunctional biocatalyst could be expressed in high amounts in Escherichia coli and was able to oxidize indole and indole derivatives into a variety of indigo compounds. The monooxygenase also performs the sulfoxidation of a wide range of prochiral sulfides, showing moderate to good enantioselectivities in forming chiral sulfoxides.  相似文献   

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