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1.
周宏杰  傅宏祥 《分子催化》1991,5(3):268-271
众所周知,酯是重要的精细化工产品。有些酯可作水果香精,有些酯是高级酒香的重要成分,己二酸二辛酯和癸二酸二辛酯则是高级增塑剂。通常,酯是用羧酸和醇反应制得。若能利用来自石油化工厂的烯烃和CO代替得之不易的羧酸来生产酯类。将具有明显的实际意义。国外曾试探过许多过渡金属包括钴、铑、铱等的配位催化体系对烯烃进行氢酯基化的催化反应,其中以钯膦体系效果最佳。国内,已有二、三个研究小组对钯膦体系进行探索,但未见有关钯膦酸催化剂体系方面的报道。本文介绍我们在钯膦酸体系催化氢酯基化反应的一些实验结果。  相似文献   

2.
考察了手性双膦配体DDPPI在钯催化1-辛烯及官能化端烯的不对称氢酯基化反应中的手性诱导作用,最高得到了45.2%的ee值.其中在1-辛烯的不对称氢酯基化反应中,考察了不同的膦-钯比、反应温度、压力、不同的溶剂、不同的钯催化剂前体以及助催化剂对反应的影响.其中膦,钯比在2~4的范围内,催化反应获得了较高的光学产率;以丙酮作溶剂,得到较好的催化效果.  相似文献   

3.
烯烃氢酯基化反应是羰基合成领域的重要分支之一,长期以来一直备受关注。目前已发展了钯基、铑基、钴基、钌基等众多催化体系,其中钯-膦-酸催化体系因具有反应条件温和、底物普适性良好、催化性能优异等优点而得到最广泛、最深入的研究。因此,我们对均相、非均相的钯-膦-酸催化体系在烯烃氢酯基化反应中的研究应用进行了简要综述,并对催化机理、催化剂组成和性能进行讨论,最后指出稳定性高、可回收性好的非均相钯-膦-酸催化体系将是该领域的研究重点。  相似文献   

4.
研究了以PdCl2-CuCl2-PPh3为催化剂体系,甲基乙基酮、乙二醇二甲醚为溶剂,苯乙烯与一氧化碳及甲醇立体选择生成2-苯基丙酸甲酯的反应.对不同的催化剂前体催化烯烃氢酯基化反应进行了研究,得知CuCl2在此催化反应中起着立体控制作用.同时考察了影响反应的各种因素如溶剂、反应温度、反应压力、不同的膦配体等.实验结果表明,该反应的最佳条件是:反应温度80℃,反应压力4.0—6.0MPa,反应时间24h,最好的溶剂是乙二醇二甲醚及甲基乙基酮.利用该催化剂体系对不同结构的烯烃催化反应进行了研究,发现该体系仅仅对苯乙烯类有较高的立体选择催化活性  相似文献   

5.
铑-膦配位催化烯烃氢甲酰化反应研究   总被引:7,自引:1,他引:6  
本文研究了由Rh2(CO)4CI2分别与两种膦配体4-下丁苯基二苯基膦(1)和4-正辛苯基二苯基磷(2)形成的原位催化剂体系对烯烃氢甲酰化反应的催化性能。对影响反应的各种因素,如P/Rh物质的量比、反应温度、反应压力,不同烯烃等的影响作了探讨。结果表明,配体1、2与Rh2(CO4)CI2形成的原位催化剂体系的催化活性与选择性均高于结构相似的PPh3,在相同的条件下,不同烯烃的氢甲酰化反应活性依直链烯烃>苯乙烯>直链内烯>环己烯的顺序递增。  相似文献   

6.
以甘露醇和山梨醇为原料,合成了2个新的手性膦配体,并用这些新的手性膦配体与钯原位生成的催化剂体系催化苯乙烯的不对称氢酯基化反应,得到R构型的2-苯基丙酸甲酯,其ee值分别为28.5%和13.6%。  相似文献   

7.
钯-手性膦催化降冰片烯的不对称氢酯基化反应   总被引:4,自引:0,他引:4  
首次用Pd(OAc)2-1,4∶3,6-双脱水-2,5-二(二苯基膦)-L-艾杜糖醇(DDPPI)-p-TsOH催化体系对降冰片烯进行了不对称氢酯基化反应,获得了较好的结果.考察了手性膦配体的结构以及磷原子与钯原子的摩尔比对反应的影响,发现在一个磷原子配位一个钯原子时,获得了较高的光学产率.同时考察了反应温度、反应压力及溶剂对降冰片烯不对称氢酯基化反应的影响,发现在120℃,5.0MPa,n(P)/n(Pd)=1时,化学产率可达71.6%,光学产率可达92.2%.  相似文献   

8.
合成了四膦配体C(CH2PPh2)4,并研究了由钴-四膦配体组成的催化剂体系对烯烃氢甲酰化反应的催化作用.对反应的各种因素,如反应温度、反应压力、不同P/Co比,不同烯烃等的影响作了探讨,并与不同膦配体体系催化烯烃氢甲酰化作对比,发现膦配体催化活性有如下顺序:C(CH2PPh2)4≈Ph2P(CH2)2PPh2>Ph2P(CH2)3PPh2>Ph2PCH2PPh2>Ph2P(CH2)4PPh2.  相似文献   

9.
PdCl2—CuCl2—手性膦催化苯乙烯不对称氢酯基化反应   总被引:4,自引:1,他引:3  
周宏英  侯经国 《分子催化》1997,11(6):408-412
首次将PdCl2-CuCl2-手性磷催化体系用于苯乙烯不对称氢酯基化反应,获得了非常好的结果,在此不对称氢酯基化反应中,考察了手性配体的结构及磷原子与钯原子的摩尔比对反应的影响,在P/Pd=2-4的范围内,获得了较高的光学产率;  相似文献   

10.
PdCl2—CuCl2—PPh3催化剂立体选择催化烯烃氢酯基化反应   总被引:4,自引:4,他引:0  
周宏英  傅宏祥 《分子催化》1996,10(6):407-412
研究了以PdCl2-CuCl2-PPh3为催化剂体系,甲基乙基酮、乙二醇二甲醚为溶剂,苯乙烯与一氧化碳及甲醇立体选择生成2-苯基丙酸酯的反应,对不同的催化剂前体催化烯烃氢酯基化反应进行了研究,得知CuCl2在此催化反应中起着立体控制作用,同时考察了影响反应的各种因素如溶剂、反应温度、反应压力、不同的膦配体等,实验结果表明,该反应的最佳条件是:反应温度80℃,反应压力4.0-6.0MPa反应时间24  相似文献   

11.
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.  相似文献   

12.
KMnO4-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.  相似文献   

13.
The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.  相似文献   

14.
Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.  相似文献   

15.
An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.  相似文献   

16.
A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.  相似文献   

17.
The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp3)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp2)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp2)?H and aliphatic 1,5- and 1,6-C(sp3)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp3)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp2)?H insertion.  相似文献   

18.
The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.  相似文献   

19.
20.
Quercetin, the polyphenolic compound, which has the highest daily intake, is well known for its protective effects against aging diseases and has received a lot of attention for this reason. Both quercetin 3-O-β-d-glucuronide and quercetin 3′-O-β-d-glucuronide are human metabolites, which, together with their regioisomers, are required for biological as well as physical chemistry studies. We present here a novel synthetic route based on the sequential and selective protections of the hydroxyl functions of quercetin allowing selective glycosylation, followed by TEMPO-mediated oxidation to the glucuronide. This methodology enabled us to synthesize the five O-β-d-glucosides and four O-β-d-glucuronides of quercetin, including the major human metabolite, quercetin 3-O-β-d-glucuronide.  相似文献   

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