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1.
The enantioselective Diels-Alder reaction is one of the most important reactions for the synthesis of complex molecules. It provides access to chiral six-membered carbocyclic compounds containing up to four stereogenic centers in a single step. Asymmetric catalysis in the Diels-Alder reaction has mainly been realized using chiral Lewis acids. In this perspective, we describe several cases of chiral Br?nsted-acid and Br?nsted-base catalyzed Diels-Alder reactions, providing an overview of this rapidly growing field. 相似文献
2.
It has been suggested [F. H. Stillinger, J. Chem. Phys. 112, 9711 (2000)] that the convergence or divergence of M?ller-Plesset perturbation theory is determined by a critical point at a negative value of the perturbation parameter z at which an electron cluster dissociates from the nuclei. This conjecture is examined using configuration-interaction computations as a function of z and using a quadratic approximant analysis of the high-order perturbation series. Results are presented for the He, Ne, and Ar atoms and the hydrogen fluoride molecule. The original theoretical analysis used the true Hamiltonian without the approximation of a finite basis set. In practice, the singularity structure depends strongly on the choice of basis set. Standard basis sets cannot model dissociation to an electron cluster, but if the basis includes diffuse functions then it can model another critical point corresponding to complete dissociation of all the valence electrons. This point is farther from the origin of the z plane than is the critical point for the electron cluster, but it is still close enough to cause divergence of the perturbation series. For the hydrogen fluoride molecule a critical point is present even without diffuse functions. The basis functions centered on the H atom are far enough from the F atom to model the escape of electrons away from the fluorine end of the molecule. For the Ar atom a critical point for a one-electron ionization, which was not previously predicted, seems to be present at a positive value of the perturbation parameter. Implications of the existence of critical points for quantum-chemical applications are discussed. 相似文献
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Song W Marcus DM Abubakar SM Jani E Haw JF 《Journal of the American Chemical Society》2003,125(46):13964-13965
Framework-bound alkoxy groups are well-studied intermediates in zeolite chemistry, but their low stability complicates their spectroscopic study in high-temperature reactions such as alkylation or dealkylation. Taking advantage of the much higher bond strength of Si-O versus C-O, we synthesized trimethylsilylated zeolites by reacting them with phenyltrimethylsilane in a catalytic flow reactor at 648 K. In favorable cases, the reaction accurately titrated the acid sites, and 29Si and 13C MAS NMR spectra of the derivatized catalysts measured at room temperature confirmed the proposed reaction. 相似文献
5.
Telalović S Ng JF Maheswari R Ramanathan A Chuah GK Hanefeld U 《Chemical communications (Cambridge, England)》2008,(38):4631-4633
Synergy between Br?nsted acid sites and Lewis acid sites in mesoporous Al-Zr-TUD-1 was demonstrated to exist in Br?nsted acid catalysed reactions, but not in Lewis acid catalysed reactions. 相似文献
6.
Rate acceleration of the addition of benzyl azide to an electron deficient olefin is characterized using in situ IR spectroscopy. Under strictly anhydrous conditions and at depressed temperature (-20 degrees C), a triazoline intermediate is selectively formed. The stability of this protonated triazoline intermediate at -20 degrees C is indefinite, but warming of the reaction mixture to 0 degrees C or above results in its conversion to the beta-amino oxazolidine dione observed under conditions used in our earlier report. As an alternative to warming, the same conversion can be effected by the addition of a single equivalent of water. Our experiments collectively demonstrate the metastability of the protonated triazoline intermediate and secondary catalysis of triazolinium ring fragmentation by water. This behavior is attributed to the ability of water to transfer a proton from N3 to N1 of the triazoline, thereby allowing ring fragmentation and nitrogen expulsion. 相似文献
7.
(17)O-(1)H double resonance NMR spectroscopy was used to study the local structure of zeolite H-Mordenite. Different contact times were used in cross-polarization magic angle spinning (CPMAS) NMR, CP rotational-echo double resonance (CP-REDOR) NMR, and heteronuclear correlation (HETCOR) NMR spectroscopy to distinguish between Br?nsted acid sites with different O-H distances. The accessibility of the various Br?nsted acid sites was quantified by adsorbing the basic probe molecule trimethylphosphine in known amounts. On the basis of these experiments, locations of different Br?nsted acid sites in H-Mordenite (H-MOR) were proposed. The use of (17)O chemical shift correlations to help assign sites is discussed. 相似文献
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Rosenholm JM Czuryszkiewicz T Kleitz F Rosenholm JB Lindén M 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4315-4323
The concentration and Br?nsted acidity of surface silanol groups on mesoporous silica (SBA-15) has been studied by following the adsorption of benzylamine, BA, from water as a function of pH. The adsorbed amount of BA from water was compared to the maximum amount of BA that could be adsorbed from cyclohexane. Furthermore, the surface concentration and acidity of carboxylic acid functions on surface-functionalized SBA-15 was also studied, which allowed the relative surface concentration of remaining silanols to be obtained. Two types of silanols can be identified, where about 1/5 of the silanols have a pKa = 2 and the remaining 4/5 of the silanols have a pKa of about 8.2. According to the literature, these two types of silanols can be identified as Q3 and Q2 silanols, respectively, of which the Q3 silanols are more acidic. For the surface-functionalized materials, pKa values close to their respective intrinsic values are found for the carboxylic acid functions. However, irrespective of the method of surface functionalization, 50% or more of the accessible surface groups are silanols. The results thus suggest that the effective charge density is largely controlled by the (de)protonation of the silanol groups even for surface-functionalized mesoporous silica, which render the surface chemistry of the surface-functionalized silicas to be radically different from what simple schematic representations would suggest. The results are suggested to be of importance for reaching a predictive level of understanding for the behavior of mesoporous silica in a range of applications, as many of the foreseen applications for mesoporous silica involves water as the medium. 相似文献
10.
Electronic factors essential for NO activation by Cu(I) sites in zeolites are investigated within spin-resolved analysis of electron transfer channels (natural orbitals for chemical valence). NOCV analysis is performed for three DFT-optimized models of Cu(I)?CNO site in ZSM-5: [CuNO]+, (T1)CuNO, and (M7)CuNO. NO as a non-innocent, open-shell ligand reveals significant differences between independent deformation density components for ?? and ?? spins. Four distinct components are identified: (i) unpaired electron donation from NO ????* antibonding orbital to Cus,d; (ii) backdonation from copper d yz to ????* antibonding orbital; (iii) donation from occupied ???? and Cu d xz to bonding region, and (iv) donation from nitrogen lone-pair to Cus,d. Channel (i), corresponding to one-electron bond, shows-up solely for spin majority and is effective only in the interaction of NO with naked Cu+. Channel (ii) dominates for models b and c: it strongly activates NO bond by populating antibonding ??* orbital and weakens the N?CO bond in contrast to channel (i), depopulating the antibonding orbital and strengthening N?CO bond. This picture perfectly agrees with IR experiment: interaction with naked Cu+ imposes small blue-shift of NO stretching frequency while it becomes strongly red-shifted for Cu(I) site in ZSM-5 due to enhanced backdonation. 相似文献
11.
《中国化学快报》2023,34(8):108080
Due to the high local concentration of substrates in confined space, porous solid Brønsted acids have been extensively explored for efficient acid-catalyzed reaction. However, the porous structures with strong Brønsted acids lack long-term stability due to chemical hydrolysis. Moreover, the products inhibition effect in confined rigid cavities severely obstructs subsequent catalysis. Here, tubular Brønsted acid catalyst with unique recognition of protons was presented by self-assembly of pH-responsive aromatic amphiphiles. The responsive assembly could mechanically transfer hydrogen ions from low-concentration acidic solution into tubular defined pores, thereby producing effective catalytic activity for Mannich reactions in mildly acidic solution. Notably, the tubular catalyst unfolded into flat sheets upon addition of triethylamine for efficient release of products, which could be recovered by subsequent acidification and the catalytic activity still remained. Therefore, the porous Brønsted acid with reversible assembly provides a new strategy for mass synthesis through increasing conversion times. 相似文献
12.
Mihai C Kravchuk AV Tsai MD Bruzik KS 《Journal of the American Chemical Society》2003,125(11):3236-3242
Phosphatidylinositol-specific phospholipase C cleaves the phosphodiester bond of phosphatidylinositol to form inositol 1,2-cyclic phosphate and diacylglycerol. This enzyme also accepts a variety of alkyl and aryl inositol phosphates as substrates, making it a suitable model enzyme for studying mechanism of phosphoryl transfer by probing the linear free-energy relationship (LFER). In this work, we conducted a study of Br?nsted-type relationship (log k = beta(lg) pK(a) + C) to compare mechanisms of enzymatic and nonenzymatic reactions, confirm the earlier proposed mechanism, and assess further the role of hydrophobicity in the leaving group as a general acid-enabling factor. The observation of the high negative Br?nsted coefficients for both nonenzymatic (beta(lg) = -0.65 to -0.73) and enzymatic cleavage of aryl and nonhydrophobic alkyl inositol phosphates (beta(lg) = -0.58) indicates that these reactions involve only weak general acid catalysis. In contrast, the enzymatic cleavage of hydrophobic alkyl inositol phosphates showed low negative Br?nsted coefficient (beta(lg) = -0.12), indicating a small amount of the negative charge on the leaving group and efficient general acid catalysis. Overall, our results firmly support the previously postulated mechanism where hydrophobic interactions between the enzyme and remote parts of the leaving group induce an unprecedented negative-charge stabilization on the leaving group in the transition state. 相似文献
13.
The role of Lewis and Brønsted acid sites in the Diels-Alder cycloaddition (DAC) of ethylene to 2,5-dimethylfuran (2,5-DMF) to p-xylene was investigated. Amorphous silica catalysts containing Al3+ (ASA), Ga3+ (ASG), and In3+ (ASI) were prepared via homogeneous deposition-precipitation. Silica modified with Zr4+ (ASZ) was prepared by impregnation. Their acidic properties were characterized by various IR and NMR spectroscopic techniques. Measurements using pyridine as a probe molecule highlighted the presence of mostly Lewis acid sites (LAS) in all materials. Using CO as a probe, in contrast, demonstrated the existence of Brønsted acid sites (BAS) in ASA and ASG, which were nearly absent in ASI and ASZ. Differences in basic strength can explain the contrast in results observed between the two probe molecules. The highest p-xylene yield (~20 %) in the DAC reaction, could be achieved with ASA and ASG. The lack of BAS in ASI and ASZ resulted in inferior performance in the DAC, with p-xylene yields below 5 %. These results indicate the importance of BAS for the DAC reaction. Several other heterogeneous and homogeneous catalysts were explored for the DAC reaction to show the generality of our conclusion that BAS play a critical role in obtaining p-xylene from 2,5-DMF and ethylene. 相似文献
14.
Rõõm EI Kütt A Kaljurand I Koppel I Leito I Koppel IA Mishima M Goto K Miyahara Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(27):7631-7643
A comprehensive basicity study of alpha,omega-alkanediamines and related bases has been carried out. Basicities in acetonitrile (AN, pK(a) values), tetrahydrofuran (THF, pK(alpha) values), and gas phase (GP, GB values), were measured for 16, 14, and 9 diamine bases and for several related monoamines. In addition the gas-phase basicities and equilibrium geometries were computed for 19 diamino bases and several related monoamines at the DFT B3LYP 6-311+G** level. The effects of the different factors (intrinsic basicity of the amino groups, formation of intramolecular hydrogen bonds, and molecular strain) determining the diamine basicities were estimated by using the method of isodesmic reactions. The results are discussed in terms of molecular structure and solvation effects. The GP basicity is determined by the molecular size and polarizability, the extent of alkylation, and the energy effect of intramolecular hydrogen bond formation in the protonated base. The basicity trends in the solvents differ very much from those in GP: 1) The solvents severely compress the basicity range of the bases studied (3.5 times for the 1,3-propanediamine family in AN, and 7 times in THF), and 2) while stepwise alkylation of the basicity center leads to a steady basicity increase in the gas phase, the picture is complex in the solvents. Significant differences are also evident between THF and AN. The high hydrogen bond acceptor strength of THF leads to this solvent favoring the bases with "naked" protonation centers. In particular, the basicity order of N-methylated 1,3-propanediamines is practically inverse to that in the gas phase. The picture in AN is intermediate between that of GP and THF. 相似文献
15.
High-resolution 17O/1H double resonance NMR spectra were obtained for two zeolites, one with a low Si/Al ratio (zeolite HY) and one with a high Si/Al ratio (HZSM-5), to investigate their local structure and Br?nsted acidity. Two different oxygen signals, corresponding to Br?nsted acid sites in supercages and sodalite cages of zeolite HY were readily resolved in the two-dimensional (2-D) 1H-17O heteronuclear correlation (HETCOR) NMR spectra allowing the 17O isotropic chemical shift (deltaCS) and quadrupolar coupling parameters (quadrupolar coupling constant, QCC, and asymmetry parameter, eta) for the two oxygen atoms to be extracted. Similar experiments for HZSM-5 showed that the sites in this system are associated with a much larger distribution in NMR parameters than found in HY. 17O-1H rotational echo double resonance (REDOR) NMR was applied to probe the O-H distances in zeolites HY and HZSM-5. Weaker 17O-1H dephasing was observed for zeolite HZSM-5 in comparison to that of HY, consistent with longer O-H bonds and/or increased proton mobility. 相似文献
16.
Comparative analysis of the specific features of autooxidation of ferrocenylacetic acid (FcCH2COOH) in organic solvents at 30–50°C in the absence and in the presence of trifluoroacetic acid (processes 1 and 2 respectively)
was carried out. It was shown that both reactions proceed as a sequence of two macrostages, the molecular and the chain radical
oxidation of the metal complex. Introduction of acid (HX) in the reaction mixture leads to a significant increase in the rate
of the process, in the amount of oxygen per one mole of metal complex absorbed by the reaction mixture, and to the change
in the yields of main reaction products like hydroxymethylferrocene, formylferrocene, ferrocenylpyruvic acid, and CO2. On the basis of results of the investigation performed, the kinetic and thermodynamic analysis of primary reactions of the
process probable mechanisms of both macrostages in both processes were suggested. The significant effect of approach and orientation
on the rate of the molecular oxidation of complex as the bifunctional reagent was noted. An assumption was made that the acid
takes place in the molecular oxidation of FcCH2COOH according to two alternative mechanisms differing by the way of its coordination with O2 and the metal complex in the prereactional intermediates. The oxidative transformation of these intermediates leads to the
generation of radicals of different nature, Fc+·CH2C(O)OO· and HO2· which initiate the chain radical oxidation of the metal complex. 相似文献
17.
Kondo JN Ito K Yoda E Wakabayashi F Domen K 《The journal of physical chemistry. B》2005,109(21):10969-10972
Acid-catalyzed ethanol dehydration on zeolite is shown to proceed via a covalent ethoxy group (C2H5O) as a stable intermediate, which was directly observed by IR spectroscopy. 相似文献
18.
Zheng A Han B Li B Liu SB Deng F 《Chemical communications (Cambridge, England)》2012,48(55):6936-6938
Solid-state NMR and DFT calculation studies certified the presence of an intermolecular solvent effect for molecules confined in microporous zeolite, leading to a notable increase in Br?nsted acidity of the solid acid catalyst. 相似文献
19.
Borghèse S Blanc A Pale P Louis B 《Dalton transactions (Cambridge, England : 2003)》2011,40(6):1220-1223
Based on H/D isotope exchange studies devoted to the quantification of the number of Br?nsted acid sites in solid acids, we report herein an innovative approach to determine the amount of silver cations present in Keggin-type polyoxometalates (POM). The molecular design of these bifunctional heteropolyacids can therefore be achieved by varying the Ag(+)versus H(+) exchange ratio in the starting mixture. Consequently, the stoichiometries of Ag(x)H(4-x)SiW??O?? POM were ascertained for 0 < x < 4 by the H/D exchange technique. 相似文献
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