药物中间体电合成技术的研究与应用

综述了药物中间体电合成技术的研究，从直接电合成、间接电合成、成对电合成及超声电合成法四个方面介绍了电合成技术在药物中间体合成中的应用。参考文献43篇。     

手性2-取代哌嗪类药物中间体的合成进展

手性2-取代哌嗪是一类重要的医药中间体,在药物合成领域有着广阔的应用前景。本文概述了当前手性2-取代哌嗪的合成方法。     

含氟苯硼酸的合成及应用研究进展

含氟苯硼酸是一种重要的有机合成中间体, 在有机合成中应用相当广泛. 综述了近年来含氟苯硼酸的合成及应用方面的重要研究进展.     

有机小分子不对称催化Michael加成的研究进展

有机小分子催化成为现在最热门的研究领域之一.不对称Michael加成反应是合成具有一个或多个手性中心合成砌块和药物中间体的重要方法.介绍了近3年来有机小分子伯胺衍生物、吡咯烷衍生物、(硫)脲、手性方酰胺和磷酸等在不对称催化Michael加成中的应用研究进展.对各种小分子结构和催化活性的关系、催化剂诱导活化机理以及各种催化体系在药物和关键中间体合成中的应用也进行详细的评述.     

酰基膦酸酯的合成及其在有机合成中的应用研究进展

酰基膦酸酯是一类活泼的有机合成中间体。本文归纳介绍了此类化合物的合成方法以及其近年来在有机合成中的应用。     

腈水解酶在医药中间体生物催化研究中的最新进展

腈水解酶是生物催化领域中的一种重要催化剂,可用于羧酸的生物合成,反应过程具有条件温和、催化效率高、选择性突出、工艺绿色环保等特点,在医药中间体的制备中具有重要应用,符合原子经济性和绿色化学的发展方向。相关酶种的挖掘及改造已逐步成为新的研究热点,许多腈水解酶催化剂已被开发应用于医药中间体的合成。随着现代分子生物学技术的进步以及生物催化进入第三次发展浪潮,利用基因工程手段构建的基因工程菌或纯化酶作为催化剂已变得较为普遍,提高催化剂的催化潜力、改善其催化特性以最大程度的体现腈水解酶合成反应的独特优势,将为腈水解酶应用于更多医药中间体的合成奠定基础。本文综述了用于医药中间体合成的腈水解酶的应用与发展现状,并探讨了该领域研究所面临的前所未有的机遇与挑战。     

经由氮杂邻联烯醌中间体合成轴手性化合物的研究进展

轴手性化合物不仅是不对称合成领域重要的催化剂和配体,许多天然产物和药物也是轴手性化合物.因此,发展轴手性化合物的高效合成方法是有机化学的重要研究课题.相对已经被广泛研究的邻联烯醌中间体,基于氮杂邻联烯醌中间体的不对称催化反应近年来才受到人们的关注,研究相对较少,有着很大的发展空间.总结了经由氮杂邻联烯醌中间体构建轴手性化合物的研究进展,介绍了反应范围、机理和合成应用.最后对该研究领域的发展前景进行了总结和展望.     

固体超强酸S2O8^2-/ZrO2-SiO2-Sm2O3催化合成溴代正辛烷的研究

溴代正辛烷是重要的有机精细化工产品中间体[1],主要用于合成脂肪醇聚氧乙烯醚,烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚硫酸盐等表面活性剂;也是合成菌毒清的中间体.     

环戊二烯衍生物的合成及应用研究进展

环戊二烯及其衍生物是一类重要的小分子环烯烃化合物,在金属茂化合物合成、有机中间体合成和有机光电材料等领域具有重要应用价值.结合本课题组的研究成果,主要综述环戊二烯衍生物的合成研究进展,并介绍一些典型的环戊二烯衍生物在有机合成领域应用研究进展.     

阿洛西林合成中间体咪唑酰氯含量的测定

阿洛西林是目前临床应用的一种广谱青霉素类抗生素，尤其对绿脓杆菌感染有效，咪唑酰氯（Ⅰ）是合成该抗生素的关键中间体。它的含量对产物的合成收率和质量具有密切的关系，是生产过程中关键的质量控制点，需要一种简便快速的测定方法进行质量监控。本工作介绍该中间体咪唑酰氯含量的测定方法，该操作程序仅需盐酸液标化，方法不需要标准对照品，能排除成品中有关杂质的干扰，操作简便，用时少，能满足该中间体的质量控制要求。     

Synthesis of new heterocyclic derivatives of retinoids

Reaction of α- and β-ionones 1 and 2 with dialkylformamide/phosphorus oxychloride affords enamines 6 and 7 along with the expected chloro derivatives 4 and 5 . Reaction of 6a with hydrazines, hydroxylamine and guanidine furnished pyrazoles, isoxazole, pyrimidine 8–10 showing the potential of these enaminones as key intermediates in the synthesis of synthetic retinoids.     

Synthesis of Functionalized α‐Vinyl Aldehydes from Enaminones

An efficient Rh^II‐catalyzed synthesis of functionalized α‐vinyl aldehydes with high E/Z stereoselectivity was developed. The reaction mediates the cyclopropanation of enaminones with vinyl carbenoids that are generated from cyclopropenes in situ to give the aminocyclopropane intermediates. Selective C?C bond cleavage of the cyclopropane intermediates leads to formation of α‐vinyl aldehyde derivatives with high E/Z selectivity. This method proceeds at room temperature under very mild reaction conditions and works with a broad substrate scope.     

Synthesis of some novel 11b-substituted pyrimido[6,1-a]-isoquinoline derivatives

A series of novel 11b-substituted 1,6,7,11b-tetrahydropyrimido[6,1-a]- isoquinoline-2,4-diones and 4-thioxo-1,3,4,6,7,11b-hexahydropyrimido[6,1-a]isoquinolin-2- ones were synthesized, utilizing two alternative strategies for ring closure of tetrahydroisoquinoline intermediates obtained from N-phenethyl enaminones.     

Simple and Efficient One‐Pot,Three‐Component,Solvent‐Free Synthesis of β‐Enaminones via Sonogashira Coupling–Michael Addition Sequences

A simple, efficient, and environmentally friendly one‐pot, three‐component synthesis of β‐enaminones via Sonogashira coupling–Michael addition sequences under solvent‐free conditions has been reported. Also the synthesis of β‐enaminones has been achieved in high yields by the direct reaction of amines with ynones under solvent‐free conditions.     

Synthesis of 3-keto-quinolines from enaminones,anilines and DMSO: Transition metal free one pot cascade

An efficient and transition metal-free approach for the synthesis of functionalized 3-ketoquinolines from readily available anilines, enaminones and DMSO in the presence of K₂S₂O₈ has been conducted. This one pot tandem reaction proceeds through [3+2+1] cycloaddition reaction involving DMSO, enaminones and amines. In this environmental benign approach, DMSO acts as both a one carbon source and the solvent. A broad range of variously substituted amines and enaminones are successfully employed in this one pot tandem process to access a broad range of substituted 3-ketoquinolines.     

Selective Synthesis of Fluorine-Containing Enaminones of Benzofuran Series

Russian Journal of General Chemistry - Selective synthesis of regioisomers of fluorine-containing enaminones of the benzofuran series was carried out from benzofuranoyltrifluoroacetone according to...     

Synthesis of heterocyclic sulfonylureas

We examined the scope of the previously reported one-pot synthesis [1] of chromone-3-sulfonylureas. Different anilines and heterocyclic amines were thereby reacted with chlorosulfonyl isocyanate-derived chlorosulfonylureas. These were treated with different enaminones and enamines to provide the title compounds.     

Enaminones as Synthons for a Directed C−H Functionalization: RhIII‐Catalyzed Synthesis of Naphthalenes

The use of enaminones as effective synthons for a directed C?H functionalization is reported. Proof‐of‐concept protocols have been developed for the Rh^III‐catalyzed synthesis of naphthalenes, based on the coupling of enaminones with either alkynes or α‐diazo‐β‐ketoesters. Two inherently reactive functionalities (hydroxy and aldehyde groups) are integrated into the newly formed cyclic framework and a broad range of substituents are tolerated, rendering target products readily available for further elaboration.     

An Environmentally Benign Catalytic Method for Versatile Synthesis of 1,4-Dihydropyridines via Multicomponent Reactions

The synthesis of diverse 1,4‐dihydropyridines have been achieved via the multicomponent reactions of aldehydes, enaminones and amines. The reactions have been smoothly performed in water to provide all products with moderate to excellent yields by using lactic acid as a green catalyst.     

Studies towards the enantioselective synthesis of 5,6,8-trisubstituted amphibian indolizidine alkaloids via enaminone intermediates

Investigations aimed at the enantioselective total synthesis of indolizidine 223A, a recently described 5,6,8-trisubstituted indolizidine alkaloid from a dendrobatid frog, are described. tert-Butyl (2R,3R)-3-amino-2-ethylhexanoate and its (2S,3R)-diastereomer, prepared in several steps from lithium N-benzyl-N-[(1R)-1-phenylethyl]amide and tert-butyl (2E)-hex-2-enoate by the Davies protocol, served as chiral building blocks from which two complementary suites of diastereomeric intermediates were made en route to pivotal tert-butyl 3-[2-(alkoxycarbonylmethylene)pyrrolidin-1-yl]-2-ethylhexanoate intermediates 20 and 21. Cyclisation of these enaminones, achieved by acid hydrolysis of the tert-butyl esters and activation of the liberated carboxylic acids as mixed anhydrides, afforded 6-ethyl-7-oxo-5-propyl-1,2,3,5,6,7-hexahydroindolizine-8-carboxylate esters 28 and 29. Several further transformations of these potential scaffolds for the synthesis of the target alkaloidal systems are also reported.