共查询到17条相似文献,搜索用时 78 毫秒
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促进活性细胞催化前手性羰基不对称还原研究进展 总被引:2,自引:0,他引:2
利用活性微生物细胞催化羰基不对称还原成为手性醇合成的重要方法。虽然当前已经筛选出许多立体选择性很高的微生物和反应过程,但这类反应能实际应用的还很少,主要是因为产业化方面的研究不够。本文从此出发,结合作者近几年的研究工作对当前活性微生物细胞催化羰基不对称还原相关工程方面的研究进行了详细的介绍和论述。分析了利用活性细胞催化时空产率低的原因,对国内外研究者针对这些原因为提高时空产率所进行的各种研究和提出的方法分别进行了归纳和分析。 相似文献
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以苯乙酮(ACP)为模型底物研究了水相体系中面包酵母的不对称还原催化特性,考察了多个因素对产率及ee值的影响,确定了最佳反应条件。考察了面包酵母细胞对苯丙酮,4-氯苯乙酮,4-羟基苯乙酮,4-硝基苯乙酮等不对称还原催化效果。结果表明:产物的立体选择性受到羰基相连基团的体积和苯环上连接基团电子效应的共同作用。基团的体积差异越大,产物的立体选择性越高;苯环上吸电子基团提高产物的立体选择性,供电子基团降低产物的立体选择性。产率只同羰基相连基团体积大小有关,体积增大使反应产率降低。 相似文献
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不对称合成是当代有机合成的热点,不对称催化方法是获取单一异构手性化合物最具有前景的方法之一。本文综述了近年来用微生物和金属手性催化剂催化氢化β—酮酯的基础研究进展。 相似文献
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以酵母细胞不对称还原苯乙酮合成S-α-苯乙醇为模型反应,研究了酵母细胞催化芳香酮的不对称还原情况.首先考察了底物和产物对细胞的毒性情况及对反应的不利影响;再在此基础上研究通过引入树脂吸附控制底物和产物浓度以避免较高浓度底物和产物对细胞的毒性,进而提高反应时-空产率.实验发现苯乙酮和α-苯乙醇对酵母细胞活性具有显著的毒害,抑制反应的活性;引入树脂吸附可显著促进反应的进行,使用杭州争光树脂厂的ZG3#树脂可获得最好的效果;当使用适量的树脂时底物初始浓度即使提高到70 mmoL·L-1还可以获得较好的产物收率,这比未引入树脂吸附时的底物浓度提高了近1倍. 相似文献
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以二苯基乙二胺为原料,分别与水杨醛、3,5-二叔丁基水杨醛、3,5-二甲氧基水杨醛反应合成了3种Salen配体,并与醋酸锌组成Salen-Zn络合物催化体系,考察其对芳香酮的不对称硅氢化反应的催化性能。结果表明,叔丁基Salen-Zn络合物催化体系的催化性能最优;以苯乙酮为模板底物,确定不对称硅氢化反应的最佳条件如下:(EtO)3SiH为还原剂、THF为溶剂、反应温度为30℃、反应时间为24 h,产物苯乙醇的收率为94%、ee值为98%。底物的拓展研究表明,Salen-Zn络合物催化体系对含不同官能团的芳香酮均具有良好的催化性能。该方法提供了一种高反应活性和高对映选择性合成手性芳香醇的途径,为手性药物的不对称合成以及活性中间体的开发提供了新思路。 相似文献
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Miaomiao Zhang Hongmei Jiao Haojie Ma Ran Li Bo Han Yuqi Zhang Jijiang Wang 《International journal of molecular sciences》2022,23(20)
An operationally convenient Zn-catalyzed synthesis of alcohols by the reduction of aldehydes, ketones, and α,β-unsaturated aldehydes/ketones is reported. It is a rare example of using mild and sustainable HBpin as a reductant for catalytic reduction of carbonyl compounds in the absence of acid or base as hydrolysis reagent. The reaction is upscalable and proceeds in high selectivity without the formation of boronate ester by-products, and tolerates sensitive functionalities, such as iodo, bromo, chloro, fluoro, nitro, trifluoromethyl, aminomethyl, alkynyl, and amide. The Zn(OAc)2/HBpin combination has been also proved to be chemoselective for the C=N reduction of imine analogs. 相似文献
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The review examines the chiral amine literature from 2000–2009 (May) concerning enantioselective and diastereoselective methods for N‐acylenamide and enamine reduction, reductive amination, and imine reduction. The reaction steps for each strategy, from ketone to primary chiral amine, are clearly defined, with best methods and yields for starting material preparation and final deprotection noted. Categories of chiral amines have been defined in Section 1 to allow the reader to quickly understand whether their specific target amine falls within a difficult to synthesize, or not, structural class. Amino acids are not considered in this work. 相似文献
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Jesper Ekstrm Jenny Wettergren Hans Adolfsson 《Advanced Synthesis \u0026amp; Catalysis》2007,349(10):1609-1613
A range of ketones was efficiently reduced in the presence of catalytic amounts of lithium isopropoxide in 2‐propanol under microwave heating, with alcohol products being formed in yields up to 99 %. 相似文献
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Caterina Martin Gwen Tjallinks Dr. Milos Trajkovic Prof. Dr. Marco W. Fraaije 《Chembiochem : a European journal of chemical biology》2021,22(1):156-159
Effective procedures for the synthesis of optically pure alcohols are highly valuable. A commonly employed method involves the biocatalytic reduction of prochiral ketones. This is typically achieved by using nicotinamide cofactor-dependent reductases. In this work, we demonstrate that a rather unexplored class of enzymes can also be used for this. We used an F420-dependent alcohol dehydrogenase (ADF) from Methanoculleus thermophilicus that was found to reduce various ketones to enantiopure alcohols. The respective (S) alcohols were obtained in excellent enantiopurity (>99 % ee). Furthermore, we discovered that the deazaflavoenzyme can be used as a self-sufficient system by merely using a sacrificial cosubstrate (isopropanol) and a catalytic amount of cofactor F420 or the unnatural cofactor FOP to achieve full conversion. This study reveals that deazaflavoenzymes complement the biocatalytic toolbox for enantioselective ketone reductions. 相似文献
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以纳米二氧化锆为载体的Pd催化剂制备及还原缩合性能研究 总被引:8,自引:0,他引:8
考察了不同制备方法得到的纳米二氧化锆为载体担载Pd催化剂对丙酮还原缩合的影响。纳米二氧化锆的制备方法对二氧化锆的物理性质和催化性能有较大的影响。不同的沉淀方法、陈化环境制备的纳米ZrO2,对不同的产物有不同的选择性,其中,在母液中373K陈化的二氧化锆为载体的催化剂对二异丁基酮(DIBK)的选择性较高,为61 43%;沉淀剂滴加到盐溶液中得到的二氧化锆为载体的催化剂对甲基异丁基酮(MIBK)的选择性较高,为63 70%。催化剂的酸性和Pd分散度表征结果表明,较高的Pd分散度、合适的酸性有利于MIBK的生成,较高的Pd分散度、较强的酸性有利于DIBK的生成。 相似文献