共查询到20条相似文献,搜索用时 915 毫秒
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卤化反应是一类极其重要的有机合成反应,在实验室研究和化工生产领域占据重要地位.传统卤化反应因存在使用有毒有害试剂、反应缺乏选择性等问题而亟待改进,生物酶催化策略则为突破上述瓶颈提供了可能.自然界已经进化出多种可对有机物中催化引入卤素的卤化酶.酶催化卤化反应的突出优势在于常温常压下,可使用来源温和的卤素进行高效的催化反应.催化范围包括卤化、羟卤化、卤环合和氧化脱羧等多种具有挑战性的反应.鉴于酶催化卤化反应展示出巨大的潜力,从催化活性、酶稳定性、底物浓度、催化范围等几个方面着重介绍了卤过氧化物酶在绿色卤化反应中的最新研究进展,为进一步开发绿色的卤化酶催化卤化反应提供参考. 相似文献
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不对称催化Henry反应研究进展 总被引:2,自引:0,他引:2
Henry反应是一类重要的有机反应. 按照反应中使用催化剂的种类, 分金属络合物催化、有机小分子催化、酶催化、非均相负载催化四大类, 详细介绍了不对称催化Henry反应的研究进展. 相似文献
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Bornscheuer UT Kazlauskas RJ 《Angewandte Chemie (International ed. in English)》2004,43(45):6032-6040
Biocatalysis has expanded rapidly in the last decades with the discoveries of highly stereoselective enzymes with broad substrate specificity. A new frontier for biocatalysis is broad reaction specificity, where enzymes catalyze alternate reactions. Although often under-appreciated, catalytic promiscuity has a natural role in evolution and occasionally in the biosynthesis of secondary metabolites. Examples of catalytic promiscuity with current or potential applications in synthesis are reviewed here. Combined with protein engineering, the catalytic promiscuity of enzymes may broadly extend their usefulness in organic synthesis. 相似文献
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Chao Qian 《Tetrahedron letters》2007,48(35):6100-6104
A novel and efficient enzymatic promiscuous protocol for aza-Michael addition of aromatic N-heterocycles to α,β-unsaturated compounds has been described. The reactions were catalyzed by promiscuous zinc-active-site acylase in organic solvent at 50 °C. The strategy works with a broad range of N-heterocycles to afford the corresponding Michael adduct with good yields in several hours (0.5-6 h). This catalytic promiscuity is the first example of metal-active-site enzyme-catalyzed aza-Michael addition for aromatic N-heterocycles. 相似文献
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Esterase BioH,which is obligatory for biotin synthesis in Escherichia coli,was found to exhibit a promiscuous ability to catalyse Aldol and Knoevenagel reactions with moderate to good yields.The reaction conditions including organic solvent,molar ratio of ketone to aldehyde,enzyme amount,and reaction time were investigated to evaluate the effect of different reaction conditions on yield.Target compounds were afforded in the best yield of 91.2% for Aldol reaction and 54.7% for Knoevenagel reaction.In addition,because the enzyme could be prepared with a low cost,this protocol could provide an economic route to conduct Aldol and Knoevenagel reactions,which expand the field of enzymatic promiscuity. 相似文献
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Conversion of pyruvate decarboxylase into an enantioselective carboligase with biosynthetic potential 总被引:1,自引:0,他引:1
Meyer D Walter L Kolter G Pohl M Müller M Tittmann K 《Journal of the American Chemical Society》2011,133(10):3609-3616
Pyruvate decarboxylase (PDC) catalyzes the decarboxylation of pyruvate into acetaldehyde and CO(2) and requires the cofactors thiamin diphosphate and Mg(2+) for activity. Owing to its catalytic promiscuity and relaxed substrate specificity, PDC catalyzes carboligation side reactions and is exploited for the asymmetric synthesis of 2-hydroxy ketones such as (R)-phenylacetyl carbinol, the precursor of (-)-ephedrine. Although PDC variants with enhanced carboligation efficiency were generated in the past, the native reaction, i.e., formation of aldehydes, is heavily favored over carboligation side reactions in all these biocatalysts. We characterized an active site variant (Glu473Gln) in which partitioning between aldehyde release versus carboligation is inverted with an up to 100-fold preference for the latter pathway. Due to a defective protonation of the central carbanion/enamine intermediate, substrate turnover stalls at this catalytic stage and addition of external aldehydes leads to quantitative and enantioselective formation of 2-hydroxy ketones as shown for (R)-phenylacetyl carbinol, which is afforded with unmatched yields, rates, and purity. This protein variant thus constitutes an example for the rational design of biocatalysts with greatly enhanced accidental catalytic promiscuity by selective blockage of the native reaction and accumulation of reactive intermediates under steady-state turnover conditions. 相似文献
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催化不对称Michalel加成反应的新进展 总被引:5,自引:0,他引:5
总结了近年催化不对称Michael加成反应的新方法,包括手性金属络合物催化 的反应,呈手性Lewis酸性的手性金属络合物促进的不对称加成,手性冠醚络合物 催化的反应及其它催化反应。 相似文献
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采用等体积浸渍法制备了Pd/Al2O3和Rh-Pd/Al2O3密偶催化剂,运用H2程序升温还原、CO化学吸附和X射线光电子能谱等手段对催化剂进行了表征,并考察了催化剂对丙烷总包反应和单反应的转化活性.总包反应结果表明, Rh的添加使起燃温度和完全转化温度分别降低了23和18oC.单反应结果证明,添加Rh能提高各单反应丙烷的转化活性,尤其是有NO参与的反应.表征结果证明,掺杂Rh不仅可以抑制活性组分PdOx的烧结,提高PdOx的分散度,而且可以改变其电子状态. 相似文献
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Trimethylvinylsilane and disubstituted alkynes underwent coupling reactions in the presence of the lanthanide-originated zirconocene equivalent. Both reactions, stoichiometric and catalytic in zirconium, could be carried out; in the latter case the addition of a stoichiometric amount of AlCl3 was needed. The catalytic cycle involving bimetallic polarization and a transmetallation step has been proposed. 相似文献
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A simple and efficient method was developed for the synthesis of 2.2'-arylmethylene dicyclohexane-1,3- dione derivatives via the Knoevenagel-Michael cascade reactions of aromatic aldehydes and 1,3-cyclic diketones catalyzed by "Amano" lipase DF, which expands the application field of enzyme catalytic promiscuity. This protocol provides several advantages over the traditional chemical synthesis, such as simple work-up procedure, high yields Cup to 94%) and environmental friendliness. 相似文献
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Direct catalytic asymmetric vinylogous reaction serves as a powerful tool to introduce stereocenter(s) at the γ- or/and even more remote position(s) of the vinylogous products in an atom-economical and efficient way. A variety of direct catalytic asymmetric vinylogous reactions with broad substrate scope and mild reaction conditions has been developed. Both metal catalysis and organocatalysis contributed in this field and led to the vinylogous products in high stereoselectivity. These vinylogous reactions provided efficient pathways for the synthesis of highly functionalized optically pure compounds, especially these with potential biological activity and pharmacological activity. This digest paper mainly focuses on the most recent developments in this field, including both nucleophilic addition and nucleophilic substitution. 相似文献