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1.
Irradiation of 2-benzoyladamantane derivatives in zeolites yields the endo-cyclobutanols as the only photoproduct via a gamma-hydrogen abstraction process. The cyclobutanols readily undergo retro-aldol reaction to give delta-ketoesters. The enantiomeric excess (ee) in the endo-cyclobutanols is measured by monitoring the ee in the ketoesters. Whereas in solution the ee in the product ketoester is zero, within achiral NaY zeolite, in the presence of a chiral inductor such as pseudoephedrine, ee's up to 28% have been obtained. The influence of zeolite on several chiral esters of 2-benzoyladamantane-2-carboxylic acids has also been examined. Whereas in solution the diastereomeric excess is <15%, in zeolite the delta-ketoesters are obtained in 79% de (best examples). Ab initio computations suggest that enhancement of chiral induction within zeolites is likely to be due to cation complexation with the reactant ketone. Alkali ion-organic interaction, a powerful tool, is waiting to be fully exploited in photochemical and thermal reactions. In this context zeolites could be a useful medium as one could view them as a reservoir of "naked" alkali ions that are only partially coordinated to the zeolite walls.  相似文献   

2.
The alkali ions present in the supercages of zeolites X and Y interact with included guest molecules through quadrupolar (cation-pi), and dipolar (cation-carbonyl) interactions. The presence of such interactions can be inferred through solid-state NMR spectra of the guest molecules. Alkali ions, as illustrated in this article, can be exploited to control the photochemical and photophysical behaviors of the guest molecules. For example, molecules that rarely phosphoresce can be induced to do so within heavy cation-exchanged zeolites. The nature (electronic configuration) of the lowest triplet state of carbonyl compounds can be altered with the help of light alkali metal ions. This state switch (n pi*-pi pi*) helps to bring out reactivity that normally remains dormant. Selectivity obtained during the singlet oxygen oxidation of olefins within zeolites illustrates the remarkable control that can be exerted on photoreactions with the help of a confined medium that also has active sites. The reaction cavities of zeolites, like enzymes, are not only well-defined and confined, but also have active sites that closely guide the reactant molecule from start to finish. The examples provided here illustrate that zeolites are far more useful than simple shape-selective catalysts.  相似文献   

3.
In this article, we illustrate how one can utilize the cation embedded in a zeolite matrix to control the photophysical and photochemical behavior of guest molecules included in zeolite cages/cavities. Three aspects of cation-guest interaction are highlighted. Strong electronic interaction between the cation and the guest leads to mobilization of guests within zeolite supercages, alteration of the lowest electronic configuration (n*, *) and restriction of conformation of molecules. Less obvious to a non-photochemist is the ability of cations, depending on their atomic weight, to induce spin conversion (singlet-triplet) in molecules. Photophysical studies carried out with aromatics and photodimerization of acenaphthylene highlight this point. The power of the heavy-atom cation effect in zeolites has been demonstrated by recording phosphorescence from several olefins whose phosphorescence has not previously been recorded. Cations by their sheer size can influence the mobility of molecules within zeolites. Restriction of motion of reactive intermediates results in product selectivity in reactions as illustrated with a few examples. Properties of cations and consequently their influence can change depending on whether they are hydrated or uncoordinated to water. Aggregation of dyes and aromatics and reactivities of carbonyl compounds are influenced by water present within zeolites. We have shown in this article that zeolites can be used as unique reaction vessels for photochemical reactions.  相似文献   

4.
[structure: see text] Zeolites modified with chiral inductors serve as media for performing chiral induction during photochemical reactions of organic molecules. The photochemical behavior of achiral tropolone ethyl phenyl ether illustrates this unique feature of a zeolite.  相似文献   

5.
Photochemistry of optically pure trans-2,3-diphenyl-1-benzoylcyclopropane has been examined in isotropic solution and within zeolites. Results suggest that it isomerizes by cleavage of either the C1-C2 or C1-C3 bond. From the perspective of chiral induction, photoisomerization of cis-2,3-diphenyl-1-benzoylcyclopropane derivatives with chiral auxiliaries placed at the meta and para positions of the benzoyl group have been examined both in isotropic solution and within zeolites. Whereas in isotropic solution the chiral auxiliaries placed at the meta position exhibit very little influence during the conversion of triplet cis-2,3-diphenyl-1-benzoylcyclopropane derivatives, they have significant influence within zeolites. For example, alpha-methyl benzylamine placed at the meta position of the benzoyl group (via an amide bond) yields the trans isomer with a diastereoselectivity (de) of 71% within NaY zeolite, whereas in solution no de is obtained. The chiral induction process within zeolites depends on the nature of the alkali ion and on the presence of water. Results suggest that the chiral auxiliary is able to control the bond being cleaved (C1-C2 vs. C1-C3 bond) within a zeolite, but it is unable to do so in an isotropic solution.  相似文献   

6.
From the perspective of asymmetric induction, the photochemistry of 24 chiral esters and amides of cis-2,3-diphenylcyclopropane-1-carboxylic acid from excited singlet and triplet states has been investigated within zeolites. The chiral auxiliaries placed at a remote location from the isomerization site functioned far better within a zeolite than in solution. Generally, chiral auxiliaries with an aromatic or a carbonyl substituent performed better than the ones containing only alkyl substituents. A model based on cation-binding-dependent flexibility of the chiral auxiliary accounts for the observed variation in de between aryl (and carbonyl) and alkyl chiral auxiliaries within zeolites. Cation-dependent diastereomer switch was also observed in select examples.  相似文献   

7.
8.
The photochemistry of 31 alpha-oxoamides capable of undergoing gamma-hydrogen transfer has been examined within zeolites. These molecules, upon excitation, yield two products--a beta-lactam and oxazolidinone--in solution, both resulting from gamma-hydrogen transfer. While in benzene the major product is oxazolidinone, within an MY zeolite, the main product is a beta-lactam. In this investigation, we have focused our attention on asymmetric induction in the formation of the beta-lactam product. Two approaches--using a chiral inductor and chiral auxiliary--have been employed. While in solution, in the presence of chiral inductors, achiral alpha-oxoamides yield beta-lactams with zero enantioselectivity; within zeolites, an ee of up to 44% has been achieved. Alpha-oxoamides appended with a chiral auxiliary gave beta-lactams with less than 5% diastereoselectivity in solution while within zeolites, the same alpha-oxoamides gave the products with de's of up to 83%. Such a remarkable influence of zeolites is attributed to an alkali ion interaction with the reactant alpha-oxoamides and to the confined environment of the zeolite interior. At this stage, we have not been able to provide a model with predictive power and further work is needed to understand this valuable asymmetric induction strategy.  相似文献   

9.
Two strategies, namely chiral inductor and chiral auxiliary approaches, have been examined within zeolites with the aim of achieving asymmetric induction during the photocyclization of cyclohexadienone, naphthalenone and pyridone derivatives. Within zeolites, enantioselectivity as high as 55% and diastereoselectivity as high as 88% have been obtained. The observed stereoselectivities are significant given the fact that these reactions gave very little stereoselectivities in isotropic solution media. The results obtained on the photocyclization of dienones, naphthalenones and N-alkyl pyridones within zeolites compliment our earlier investigations on the photocyclization of tropolone derivatives, the geometric isomerization of 1,2-diphenylcyclopropanes and 2,3-diphenyl-1-benzoyl cyclopropanes, and the Norrish type II reaction of alpha-oxoamides, phenyl adamantyl ketones, phenyl norbornyl ketones and phenyl cyclohexyl ketones. With the help of these examples, we have established the importance of zeolite and its charge compensating cations in effecting asymmetric induction in photochemical reactions.  相似文献   

10.
The photochemistry and complexation with alkaline-earth metal cations of two crown-containing naphthopyrans and their crownless analogues are reported. Two types of photoreactions occur in the system, namely, the reversible formation of the open form, which is responsible for the photochromism of these compounds, and the geometric isomerization of the closed form. The photochromic properties (UV spectrum and lifetime) of the naphthopyrans do not change upon complexation with metal cations. This is explained by the specific features of the structure of the open form and by the kinetic parameters of the processes.  相似文献   

11.
Absolute asymmetric photocyclization of isopropylbenzophenone derivatives was achieved by means of a cocrystal approach. Three chiral salt crystals formed by carboxylic acid derivatives with achiral amines could be prepared by spontaneous crystallization. In the M-crystal of 4-(2,5-diisopropylbenzoyl)benzoic acid with 2,4-dichlorobenzylamine, a twofold helical arrangement occurs in a counterclockwise direction to generate the crystal chirality. Conversely, the clockwise helix exists alone in the P-crystal. Irradiation of the M-crystal at >290 nm caused highly enantioselective Norrish type II cyclization to give the (R,R)-cyclopentenol, (R)-cyclobutenol, and (R)-hydrol in a 6:3:1 molar ratio, resulting in successful absolute asymmetric synthesis, while irradiation at around 350 nm afforded the (R,R)-cyclopentenol as the sole product. The reaction proceeded via single-crystal-to-single-crystal transformation, and therefore the reaction path producing the (R,R)-cyclopentenol could be traced by X-ray crystallographic analysis before and after irradiation.  相似文献   

12.
Methods to generate triplets of organic molecules within zeolites have been established by employing the Zimmerman rearrangement of barrelenes, oxa-di-π-methane rearrangement of β,γ-unsaturated ketones and photodimerization of acenaphthylene as probe reactions. The two methods, heavy cation effect and triplet sensitization, are well established solution techniques and these work well within zeolites. The Zimmerman rearrangement of dibenzobarrelene is enhanced even within Li+ and Na+ exchanged zeolites and these are believed to be the result of slowing of the rearrangement to dibenzocyclooctatetraene from S1 through cation-π interaction. The methods described here provide an opportunity to explore the control afforded by the zeolite environment on triplet reactions.  相似文献   

13.
beta-Keto esters and beta-keto amides can be efficiently alkylated on reaction with enol ethers and manganese(III) acetate in the presence of copper(II) acetate. These intermolecular radical addition reactions can be used to construct quaternary carbon centres in excellent yield and this method has been utilised in a diastereoselective approach to substituted pyrrolidinones.  相似文献   

14.
Alkali ion-exchanged Y-zeolites significantly enhance asymmetric induction in the photoisomerization of a number of cis-1,2-diphenylcyclopropane derivatives containing a distant chiral auxiliary.  相似文献   

15.
The photochemical properties of 4-styrylquinoline and its derivatives with fluorine and chlorine atoms and nitro group in the para-position of the styryl moiety were studied. Under irradiation in neutral alcohol solutions, these compounds undergo reversible trans-cis photoisomerization with quantum yields close to 0.5, and the cis-isomers undergo cyclization to give benz[i]phenanthridines with quantum yields that do not exceed 0.01. For several compounds, the primary product of photocyclization, dihydrobenz[i]phenanthridine, was spectrally detected. On passing from the neutral to protonated forms, the photoisomerization quantum yields of these styrylquinolines changed insignificantly, and the photocyclization did not occur at all.  相似文献   

16.
17.
An efficient molybdenum-catalyzed asymmetric allylic alkylation (Mo-AAA) of cyanoester nucleophiles is reported. A number of highly functionalized branched cyanoesters containing a quaternary carbon stereocenter with a vicinal tertiary stereocenter are obtained. This method generates a number of functionalized cyanoesters in excellent yield and chemoselectivity in good to excellent diastereoselectivity and enantioselectivity.  相似文献   

18.
The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-acetate (BSP-2) and 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-carboxylate (BSP-3), differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (E(a(MC-2)) = 75.05 kJ mol(-1), E(a(MC-3)) = 100.39 kJ mol(-1)) and entropies of activation (ΔS = 43.38 J K(-1) mol(-1), ΔS = 37.78 J K(-1) mol(-1)) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K(-1) mol(-1)) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives.  相似文献   

19.
The photophysics and photochemistry of a series of naphthoxazinones have been studied using a combination of methods ranging from steady-state and time-resolved spectroscopic techniques to product analysis. The photophysics of naphthoxazinone derivatives is very dependent on the structure: phenanthrene-like compounds exhibit higher fluorescence quantum yield than the less aromatic anthracene-like homologous. The latter, exhibit a substantial degree of charge transfer in the excited singlet state. These compounds are fairly photostable in the absence of additives, yielding a single photoproduct arising from the triplet state. The presence of electron donors such as amines increases the photoconsumption quantum yield and changes the product distribution, the primary photoproduct being a dihydronaphthoxazinone that photoreacts further yielding ultimately an oxazoline derivative.  相似文献   

20.
We have developed an efficient method for the asymmetric synthesis of anti-beta-hydroxy-alpha-amino acid derivatives based on highly enantio- and diastereoselective aldol reactions of the silicon enolate derived from N-trifluoroacetylglycinate with aldehydes using a chiral zirconium catalyst. The resulting N-trifluoroacetyl group is easily cleaved under either acidic or basic conditions and can be used directly as a protecting group for further transformations.  相似文献   

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