手性5-异丙基-2-噁唑烷酮的酶催化立体选择性互补合成

以2-异丙基环氧乙烷为底物,氰酸钠为亲核试剂,筛选获得两种卤醇脱卤酶HheA10和HheG,可以分别催化合成(S)-5-异丙基-2-噁唑烷酮和(R)-5-异丙基-2-噁唑烷酮。通过对其反应条件进一步考察,建立了立体选择性互补合成手性5-异丙基-2-噁唑烷酮的生物催化技术路线。      

用芹菜茎生物催化对映选择性还原芳香酮

研究了用芹菜茎薄片在温和与环境友好的条件下催化芳香酮的对映选择性还原反应.制备得到具有光学活性的(S)-1-芳基醇,产物的对映选择性符合Prelog规则.考察了pH值、反应时间、反应温度、底物浓度等因素对底物芳香酮的转化率和产物(S)-1-芳基醇的对映体过量值的影响,并优化了这些反应条件.文中还研究了底物的构效关系,发现羰基两边取代基的空间效应和电子效应明显影响底物的转化率和产物的对映体过量值.在合适的条件下底物苯乙酮的转化率高达100%,产物(S)-1-苯基乙醇的对映体过量值大于99.0%.苯丙酮、对甲基苯乙酮和对氯苯乙酮等其它芳香酮的转化率达到中等程度,但所得(S)-1.芳基醇的最大对映体过量值均大于99.0%.     

酶催化生物可降解聚酯的合成与研究进展

生物可降解聚酯是一种新型高分子聚合材料,可通过发酵、化学方法和酶催化来合成.本文综述了酶催化下通过缩聚、酯交换、内酯开环聚合等方法合成此类聚酯.酶催化合成生物可降解聚酯是一种新型的技术,可以在温和条件下高效合成,有着传统方法难以比拟的优势.     

α-氰醇的生物催化合成新进展

总结了近10年来生物催化不对称合成α-氰醇的新进展.分别介绍了对羟腈裂解酶催化机理的新表述、反应体系(包括对酶的改造、反应介质、反应器)的新研究以及一系列醛(酮)的氢氰化反应.     

α-氰醇立体选择性合成新进展

总结了近十年来立体选择性合成α-氰醇的最新进展, 包括金属配合物催化的醛、酮类底物的立体选择性氢氰化和硅氰化反应, 不含金属的有机小分子催化剂催化的醛、酮类底物的立体选择性硅氰化反应以及生物催化的立体选择性氢氰化反应. 另外对部分反应中涉及的机理也作了介绍.     

深黄被孢霉催化转化脂肪醇合成不饱和脂肪酸的初步研究

The unsaturated fatty acids were biosynthesized by Mortierella isabellina grown on fatty alcohols (butanol, hexadecanol, octadecanol, etc) at 28 ℃ for 5 d and the fatty acid composition was analyzed by gas chromatography. The results showed that more lipid and higher content of the corresponding unsaturated fatty acids could be biosynthesized by the fungi grown on the long chain alcohols. Meanwhile, long chain alcohols were converted more quickly and had higher conversion. It suggests that long chain alcohols are more practical substrates.     

通过钯催化双C—H键活化实现“一锅”串联C—C和C—N键的形成——菲啶酮的合成

Angew.Chem.Int.Ed.2011,50,1380～1383近年来钯催化的C—H键活化已被广泛用于C—C,C—O,C—N,C—S和C—X(X=halogen)键的生成,然而一锅串联C—C和C—N键的形成极富挑战性.中国科学技术大学化学与材料科学学院王官武等通过CONHOMe导向基团实现了N-甲氧基苯甲酰胺的邻位sp~2-C—H键活化,与芳基碘代物发生芳基化,再通过sp~2-C—H键活化发生分子内关环生成具有重要生物活性的菲啶酮.该反应过程涉及到2个C—H键,1个C—I键,1个N—H键的断裂和1     

生物催化C-H键不对称羟基化反应的研究进展

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。     

生物催化在高分子合成中的应用

生物催化剂已被越来越多地用于高分子学中,产生了许多新的反应、工艺和商业用途.酶和全细胞工艺都引起了众多关注,生物催化剂的立体选择性是它们的主要优势之一,新的或改良的方法层出不穷.生物催化的进程主要集中在几个方面上:聚合反应、聚合物修饰反应、聚合物降解反应以及单体和低聚物的合成.在这篇文章中,我们总结了生物催化在高分子合成中的最新应用.     

P450酶催化C—H键官能团化的研究进展

C-H键选择性官能团化是构建C-X键最直接的策略,但因C-H键的解离能高,如何在温和条件下实现C-H键选择性官能团化是合成化学面临的巨大挑战。P450酶来源广泛,催化功能具有多样性,可催化众多反应类型,其中包括C-H键的选择性官能团化。本文主要对近十年P450酶催化C-H键羟基化、氨基化和烷基化方面进行了综述,并对其未来C-H键官能团化的研究进行了展望。      

甘油在微生物代谢合成及生物催化中的应用

生物柴油是一种可再生能源,因其可替代石油来源的柴油而日益受到重视。随着生物柴油工业的蓬勃发展,其制备过程中的主要副产物甘油出现明显的产能过剩。作为一种廉价的清洁资源,甘油的深度开发和利用既是发展生物柴油工业的关键,也符合绿色化学的发展要求。近年来,甘油不仅作为重要的起始原料用于一些高附加值化学品的制备,而且因其独特的理化性质和易降解、生物相容性好等特性,在生物催化和绿色溶剂领域的应用研究日趋活跃。本文主要综述了甘油在工业微生物发酵、生物合成和绿色溶剂领域的研究进展,并就其应用中存在的一些问题,如甘油原料品质和微生物利用效率等进行分析,同时展望了甘油在生物催化领域的应用前景。     

Applications of Ionic Liquids in Whole-Cell and Isolated Enzyme Biocatalysis

Ionic liquids have unique chemical properties that have fascinated scientists in many fields. The effects of adding ionic liquids to biocatalysts are many and varied. The uses of ionic liquids in biocatalysis include improved separations and phase behaviour, reduction in toxicity, and stabilization of protein structures. As the ionic liquid state of the art has progressed, concepts of what can be achieved in biocatalysis using ionic liquids have evolved and more beneficial effects have been discovered. In this review ionic liquids for whole-cell and isolated enzyme biocatalysis will be discussed with an emphasis on the latest developments, and a look to the future.     

生物催化产业化进展

生物催化吸引人的特征包括高效性、多样性、底物专一性、区域选择性、化学 选择性、对映选择性以及温和的反应条件．总结了一些化学公司当前在生物催化产 业化方面所取得的成就．预计在今后的十年间，将会有更多优于传统化学路线的生 物催化方法被广泛地应用于各种精细化学品的工业生产中.     

Enantioselective Chemo- and Biocatalysis: Partners in Retrosynthesis

Recent developments of stereoselective biocatalytic and chemocatalytic methods are discussed. The review provides a guide to the use of biocatalytic methods in the area of chemical synthesis with focused attention on retrosynthetic considerations and analysis. The transformations presented are organized according to bond disconnections and attendant synthetic methods. The review is expected to lead to better understanding of the characteristics and distinctions of the two complementary approaches. It depicts for researchers in bio- and chemocatalysis a road map of challenges and opportunities for the evolution (and at times revolution) in chemical synthesis.     

耐有机溶剂微生物及酶类在生物催化中的应用*

将生物催化剂运用到有机相催化具有多种优势,然而酶是一类不稳定的催化剂很容易在有机溶剂存在的条件下失去活性。耐有机溶剂微生物是一类新颖的极端微生物,它们可以在高浓度的有机溶剂存在的条件下生存,而这类微生物所产的一些酶类往往具有耐有机溶剂的性能。随着这一领域开发和发展,从这类极端微生物中寻找高效生物催化剂逐渐成为新的研究热点,并被越来越多的运用到有机相生物催化领域。本文综述了新型耐有机溶剂催化剂的开发、应用与发展,并讨论了该领域的研究所带来的机遇与挑战。     

生物催化与新药研究和开发

生物催化具有条件温和、效率高、选择性强、副产物少等特点,因此生物催化在新药的研究和开发中得到广泛的应用;此外,利用生物技术对生物催化剂进行改造优化,将使其能够更好地应用于新颖的生产工艺。本文对此领域的进展作一简单介绍和概述。     

生物催化制备香精香料

对于由细菌、真菌和酵母生产多种生物香精香料的潜力作了综述. 归纳了微生物工艺相对于化学合成或萃取的优势. 记述了由特定底物的生物转化合成香精香料. 讨论一些商业化工艺.     

Asymmetric Reductive Amination in Organocatalysis and Biocatalysis

This review summarizes the recent progress of organocatalytic and biocatalytic asymmetric reductive amination (ARA), a challenging but important topic for drug discovery and the pharmaceutical industry. At present, ARA can be divided into three categories: metal catalysis, organic catalysis, and biocatalysis. In the past decade, transition metal-catalysed ARA has been well established. Organocatalytic ARA has emerged as a powerful alternative to metal-catalysed ARA, the hydrogen sources used in organocatalytic ARA are usually Hantzsch esters, benzothiazolines, boranes, and hydrosilanes, which require Lewis base or phosphoric acid catalysts to activate them to give secondary chiral amines. It is worth mentioning that biocatalytic ARA has made remarkable progress in the last decade, amino acid dehydrogenases, amine dehydrogenases, opine dehydrogenases and imine reductases have been successfully used in ARA.     

Biocatalysis and Biomass Conversion in Alternative Reaction Media

In this Minireview, the state of the art in the use of ionic liquids (ILs) and deep eutectic solvents (DESs) as alternative reaction media for biocatalytic processes and biomass conversion is presented. Initial, proof‐of‐concept studies, more than a decade ago, involved first‐generation ILs based on dialkylimidazolium cations and non‐coordinating anions, such as tetrafluoroborate and hexafluorophosphate. More recently, emphasis has switched to more environmentally acceptable second‐generation ILs comprising cations, which are designed to be compatible with enzymes and, in many cases are derived from readily available, renewable resources, such as cholinium salts. Protic ionic liquids (PILs), prepared simply by mixing inexpensive amines and acids, are particularly attractive from both an environmental and economic viewpoint. DESs, prepared by mixing inexpensive salts with, preferably renewable, hydrogen‐bond donors such as glycerol and amino acids, have also proved suitable reaction media for biocatalytic conversions. A broad range of enzymes can be used in ILs, PILs and DESs, for example lipases in biodiesel production. These neoteric solvents are of particular interest, however, as reaction media for biocatalytic conversions of substrates that have limited solubility in common organic solvents, such as carbohydrates, nucleosides, steroids and polysaccharides. This has culminated in the recent focus of attention on their use as (co)solvents in the pretreatment and saccharification of lignocellulose as the initial steps in the conversion of second‐generation renewable biomass into biofuels and chemicals. They can similarly be used as reaction media in subsequent conversions of hexoses and pentoses into platform chemicals.