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1.
Rhodium-catalyzed hydroformylation of 1,5-hexadiene to corresponding dialdehydes was investigated using tetraphosphorus ligands. These ligands showed a high regioselectivity for linear aldehydes (linear to branch ratio up to 98%) in very good yield (up to 87%). It was found that the introduction of the substituents at the ortho position of the biphenyl moiety has little effect on the regioselectivity and the electron-donating substituents retard the reaction somewhat.  相似文献   

2.
Asymmetric, rhodium-catalyzed hydroformylation of terminal and internal aryl alkenes with diazaphospholane ligands is reported. Under partially optimized reaction conditions, high enantioselectivity (>90% ee) and regioselectivities (up to 65:1 alpha:beta) are obtained for most substrates. For terminal alkenes, both enantioselectivity and regioselectivity are proportional to the carbon monoxide partial pressure, but independent of hydrogen pressure. Hydroformylation of para-substituted styrene derivatives gives the highest regioselectivity for substrates bearing electron-withdrawing substituents. A Hammett analysis produces a positive linear correlation for regioselectivity.  相似文献   

3.
The large cone angle and bite angle of the SRS ligand diastereomer in biphenol-based Rh-bisphosphite catalysts lead to high linear regioselectivity in the hydroformylation of propylene.  相似文献   

4.
A new class of substituted tetraphosphane ligands has been developed and applied in the rhodium‐catalyzed regioselective hydroformylation of terminal olefins. The high regioselectivity (linear selectivity is above 97 % for 1‐octene and 1‐hexene) at high temperature (140 °C) shown by these tetraphosphane ligands is remarkable considering the low regioselectivity commonly observed under similar reaction conditions when other bisphosphane analogues are used. The steric and electronic effects of substituents on the diarylphosphane moiety have also been examined.  相似文献   

5.
The [HCo(CO)3]-catalyzed hydroformylation of allene and propyne has been investigated at the B3LYP level of density functional theory. It is found that hydroformylation of allene favors the linear anti-Markovnikov product in high regioselectivity both kinetically and thermodynamically. The origin of this regioselectivity comes from the enhanced stability of the eta3-allylic intermediate [(eta3-CH2CHCH2)Co(CO)3]. By contrast, propyne does not show any regioselectivity. The possible interconversion between allene and propyne mediated by [HCo(CO)3] has been explored.  相似文献   

6.
The palladium-catalyzed allylic substitution of 5-vinyloxazolidinones and derivatives was investigated. Unusual and high regioselectivity for the branched product was observed. The regioselectivity was influenced by the type of substrate, the solvents, and the nucleophile. Imide-type nucleophiles were found to be directed to the internal carbon (branched:linear, 75:25 to >98:2), whereas sulfonamides, amines, and malonates added only to the terminal carbon of the allyl complex. Relatively nonpolar solvents such as toluene and THF favored the branched product (97:3 and 95:5, respectively). Acetonitrile and dichloromethane afforded lower regioselectivity (50:50 and 67:33, respectively), and the use of the protic solvent ethanol resulted in reversal of the regioselectivity (12:88). The directing group on the substrate was important. Amides afforded almost complete formation of the branched product, and carbamates gave a 50:50 mixture of regioisomers with phthalimide as the nucleophile. Evidence for direction of the nucleophile via hydrogen bonding was obtained by replacing the hydrogen of the amide with a methyl, resulting in the production of only the normal linear product.  相似文献   

7.
We describe a method that allows salicylaldehyde derivatives to be coupled with a wide range of unactivated alkenes at catalyst loadings as low as 2 mol %. A chiral phosphoramidite ligand and the precise stoichiometry of heterogeneous base are key for high catalytic activity and linear regioselectivity. This protocol was applied in the atom- and step-economical synthesis of eight biologically active octaketide natural products, including anticancer drug candidate cytosporone B. Mechanistic studies provide insight on parameters affecting decarbonylation, a side reaction that limits the turnover number for catalytic hydroacylation. Deuterium labeling studies show that branched hydride insertion is fully reversible, whereas linear hydride insertion is largely irreversible and turnover-limiting. We propose that ligand (R(a),R,R)-SIPHOS-PE effectively suppresses decarbonylation, and helps favor a turnover-limiting insertion, by lowering the barrier for reductive elimination in the linear-selective pathway. Together, these factors enable high reactivity and regioselectivity.  相似文献   

8.
Up to 14 porphyrin rings are present in the title compounds 1 , which are readily available with high regioselectivity from linear nickel–zinc porphyrins. Upon irradiation with light a rapid energy transfer from the peripheral porphyrin rings to the diporphyrin core takes place.  相似文献   

9.
Catalytic alkane dehydrogenation is a reaction with tremendous potential for application. We describe a highly active PSCOP‐pincer iridium catalyst for transfer dehydrogenation of cyclic and linear alkanes. The dehydrogenation of linear alkanes occurs under relatively mild conditions with high regioselectivity for α‐olefin formation. In addition, the catalyst system is very effective in the dehydrogenation of heterocycles to form heteroarenes and olefinic products.  相似文献   

10.
Transition‐metal‐catalyzed hydroamination reactions are sustainable and atom‐economical C N bond‐forming processes. Although remarkable progress has been made in the inter‐ and intramolecular amination of olefins and 1,3‐dienes, related intermolecular reactions of amides are still much less known. Control of the regioselectivity without analogous telomerization is the particular challenge in the catalytic hydroamidation of alkenes and 1,3‐dienes. Herein, we report a general protocol for the hydroamidation of electron‐deficient N‐heterocyclic amides and sulfonamides with 1,3‐dienes and vinyl pyridines in the presence of a catalyst derived from [{Pd(π‐cinnamyl)Cl}2] and ligand L7 or L10 . The reactions proceeded in good to excellent yield with high regioselectivity. The practical utility of our method is demonstrated by the hydroamidation of functionalized biologically active substrates. The high regioselectivity for linear amide products makes the procedure useful for the synthesis of a variety of allylic amides.  相似文献   

11.
Transition‐metal‐catalyzed hydroamination reactions are sustainable and atom‐economical C? N bond‐forming processes. Although remarkable progress has been made in the inter‐ and intramolecular amination of olefins and 1,3‐dienes, related intermolecular reactions of amides are still much less known. Control of the regioselectivity without analogous telomerization is the particular challenge in the catalytic hydroamidation of alkenes and 1,3‐dienes. Herein, we report a general protocol for the hydroamidation of electron‐deficient N‐heterocyclic amides and sulfonamides with 1,3‐dienes and vinyl pyridines in the presence of a catalyst derived from [{Pd(π‐cinnamyl)Cl}2] and ligand L7 or L10 . The reactions proceeded in good to excellent yield with high regioselectivity. The practical utility of our method is demonstrated by the hydroamidation of functionalized biologically active substrates. The high regioselectivity for linear amide products makes the procedure useful for the synthesis of a variety of allylic amides.  相似文献   

12.
A phosphite ligand modified Rh/SiO2 catalyst has been developed for hydroformylation of internal olefins to linear aldehydes, which showed high activity and regioselectivity and could be separated easily by filtration after reaction in an autoclave. Effects of reaction temperature and syngas pressure on the performances of the catalyst in the reaction were also investigated.  相似文献   

13.
A phosphite ligand modified Rh/SiO2 catalyst has been developed for hydroformylation of internal olefins to linear aldehydes, which showed high activity and regioselectivity and could be separated easily by filtration after reaction in an autoclave. Effects of reaction temperature and syngas pressure on the performances of the catalyst in the reaction were also investigated.  相似文献   

14.
α-Carbanions of cyclic and acyclic imines have been successfully applied as nucleophiles in the Pd-catalyzed allylic alkylation reaction. Tuning of chemo- and regioselectivity has been realized by using t-BuOK/THF and LDA/toluene to give branched and linear products, respectively, with high regio- and diastereoselectivities. A plausible mechanism is proposed on the basis of the experimental results and DFT calculations.  相似文献   

15.
与芳香胺相比,芳香硝基化合物具有廉价易得、官能团兼容性好等优点,作为氮源在下游含氮化学品合成中具有广泛的应用.目前烯烃羰化酰胺化反应绝大多数以胺类化合物为氮源,其中直链和支链酰胺产物的选择性主要是通过具有特定电子和位阻特性的配体调控实现.已报道的芳香硝基化合物的还原酰胺化反应研究中,需要外加还原剂或者利用金属羰基化合物Mo(CO)6释放的CO为羰基源和还原剂.本文发展了一种毋须外加还原剂的钯催化芳香硝基化合物与烯烃的还原羰化酰胺化反应新方法.研究发现,钯金属催化剂(特别是离子型)的抗衡阴离子是还原羰化酰胺化反应中化学选择性和羰化区域选择性的关键因素.抗衡阴离子为氯离子、硼酸为助剂时,最优钯前驱物K2PdCl4的产物主要为支链酰胺,此时不同的膦配体并不能调控其区域选择性,这与胺的烯烃酰胺化反应可以通过配体调控羰化的区域选择性表现出明显的不同.含氮中间体原位捕捉、硝基化合物还原下游可能中间体对照实验等研究表明,芳香硝基化合物在以一氧化碳为还原剂的催化还原体系下被完全脱氧还原为氮烯(Ar-N:),再经过烯酰胺中间体进一步烯键还原得到相应的支链酰胺;当离子型钯前驱物的抗衡阴离子配位性较弱时,最优钯前驱物为Pd(CH3CN)4(OTf)2时,以直链酰胺为主要产物,此时不同的膦配体可以调控酰胺化的区域选择性.同样的机理研究表明,在该催化剂体系下芳香硝基化合物首先被还原为芳基胺,然后再发生与现有报道类似的胺类化合物的烯烃羰化酰胺化反应.这两个催化反应体系都表现出了较好的底物适用性,并且可以高效地应用于除草剂(敌稗)的一步合成.本文为以硝基化合物为起始氮源,通过催化控制生成特定含氮中间体,从而可控合成不同的含氮化学品提供了一条新思路.  相似文献   

16.
The ruthenium‐catalyzed hydroformylation of 1‐ and 2‐octene to give preferentially the corresponding linear aldehyde is reported. The catalyst system comprising of Ru3(CO)12 and an imidazole‐substituted monophosphine ligand allows for high chemo‐ and regioselectivity. The hydroformylation proceeds with unprecedented rates for a ruthenium‐based catalyst.  相似文献   

17.
The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX,BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system.The catalyst system HRb(CO)(PPh3)3-BISBI exhibited very hig regioselectivity for the formation of linear aldehyde.  相似文献   

18.
The regioselective three-component condensation reaction of 2-hydroxy-1,4-naphthoquinone with isocyanides in the presence of a variety of aldehydes offers an easy one-pot access to linear naphtho[2,3-b]-furan-4,9-dione derivatives. This method has the advantage of good yields, high regioselectivity, and uses readily accessible substrates and reagents. The elucidation of regiochemistry has been accomplished by X-ray determination of some representative compounds.  相似文献   

19.
制备了膦配体修饰的Rh/SiO2多相催化剂(L-Rh/SiO2),该催化剂在内烯烃氢甲酰化制备正构醛反应中表现出了高活性和高区域选择性,而且在高压釜反应器中可以通过简单的过滤与产物分离.通过使用不同的单齿和螯合双齿膦配体考察了配体的电子及空间效应对L-Rh/SiO2催化剂催化性能的影响。  相似文献   

20.
研究了双膦配体对铑催化的乙酸乙烯酯氢甲酰化反应的促进作用,结果表明,在优化反应条件下,以双膦化合物2,2’-二(二苯膦甲基)-1,1’-联苯(BISBI)为配体时,铑催化乙酸乙烯酯氢甲酰化反应的TOF(转化频率)值达到4000h1,生成2-乙酰氧基丙醛的选择性99%.当在较温和的条件下Rh/BISBI催化乙酸乙烯酯氢甲酰化反应较长时间时TON(转化数)值达到9200,成醛率超过90%,2-乙酰氧基丙醛选择性仍保持99%.  相似文献   

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