Fluorinated alcohols as solvents for diels-alder reactions of chiral acrylates

Cativiela, C.; Garcı́a, José I.; Mayoral, José A.; Royo, A. J.; Salvatella, Luis

doi:10.1016/s0957-4166(00)80368-7

Cited by 23 publications

(10 citation statements)

References 16 publications

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“…Irrespective of the menthyl group conformation, the exo approximation leads to larger diastereofacial selectivities than the endo approximation, in agreement with experimental results found for various ADA reactions. , …”

Section: Resultssupporting

confidence: 88%

Section: Resultssupporting

confidence: 85%

“…Note that for a given attacked face and conformation of the menthyl group, combined AM1/MM3 results indicate a preference for the exo approximation, which is a general trend in AM1 calculations for carbonyl dienophiles. Experimentally, the endo/exo selectivity in solution has been determined and shows that the endo structure is preferred.…”

Section: Resultsmentioning

confidence: 99%

“…Combined AM1/MM3 calculations predict in all cases that the attack through the free face is preferred over the corresponding attack through the hindered one, in agreement with experimental results. 45 This result is due to the steric repulsion between isopropyl group and cyclopentadiene. Stacked conformations lead to lower diastereofacial selectivities (compare free and hindered face energies) than those corresponding to axial and equatorial forms.…”

Section: Resultsmentioning

confidence: 99%

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The Role of Menthyl Group in Catalyzed Asymmetric Diels−Alder Reactions. A Combined Quantum Mechanics/Molecular Mechanics Study

et al. 1998

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The asymmetric Diels−Alder reactions of cyclopentadiene with the complex dienophiles AlCl3−menthyl acrylate and menthoxyaluminum dichloride−acrolein have been studied by means of combined Quantum Mechanics/Molecular Mechanics calculations. The part of the system involved in the reaction has been described using the AM1 method, whereas the MM3 force field has been used in order to account for interactions with the menthyl substituent. We focus our attention on the screening effect produced by the menthyl group, which may be placed in the dienophile or the catalyst. A reaction model has been proposed for the cycloaddition between cyclopentadiene and acrolein catalyzed by menthoxyaluminum dichloride, presenting different geometrical features from those proposed for an analogous reaction. Results indicate that the menthyl group adopts a stacked conformation preferentially, in contrast with previous Molecular Mechanics studies of similar systems. The weak steric hindrance of this conformation allows us to explain the rather low screening effect of the menthyl group. Finally, our results show that the use of the combined AM1/MM3 methodology avoids the artifactual stabilizations of nonbonded hydrogen atom pairs found in full AM1 calculations.

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Section: Resultssupporting

confidence: 88%

Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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The Role of Menthyl Group in Catalyzed Asymmetric Diels−Alder Reactions. A Combined Quantum Mechanics/Molecular Mechanics Study

et al. 1998

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“…1,2 In the last few years, several experimental and theoretical works dealing with the effect of solvent on many reactions have been published. [3][4][5] Most of these papers are concerned with the effect of solvent on reaction rates. There is surprisingly little work, involving the effect of solvent on the thermodynamics and complexation of some biologically important ligands.…”

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confidence: 99%

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

2005

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The development of various kinds of approaches to hydrophobic hydration is necessary for a better understanding of its key role in controlling biochemical processes in water. 1,2 In the last few years, several experimental and theoretical works dealing with the effect of solvent on many reactions have been published. [3][4][5] Most of these papers are concerned with the effect of solvent on reaction rates. There is surprisingly little work, involving the effect of solvent on the thermodynamics and complexation of some biologically important ligands. [6][7][8] Various empirical solvent polarity parameters have been used to describe the influence of solvents on physicochemical solute properties. 9One particularly useful set consists of complementary Lewis acid-base solvent parameters, now known for most common organic solvents.10,11 It was found for example, by analysis of the variation of Kamlet-Taft's, β and α values, 12 for mixtures of methanol and other organic solvents, that one important factor influencing the basicity or acidity of solvent mixtures is due to an order/disorder process, particularly in binary mixtures of protic solvents with non-hydrogen bond donor (non-HBD) solvents. 12,13 Nucleotides play a key role in almost all kinds of metabolic processes. Much effort was devoted to the complexes of AMP, adenosine 5′-monophosphate, with metal ions. The properties and structures of binary complexes of most metal ion-AMP systems in aqueous solution are now relatively well described.14,15 Depending on the kind of metal ion involved, coordination occurs not only to the phosphate chain but also to N-1, leading thus to macrochelates.Thallium has been recognized as a toxic element for many years. It produces a variety of adverse effects in human beings. This element acts on the central nervous system and induces an inflammatory response. 16,17 However, the metabolic action and mechanism and fate of thallium toxicity are still not well understood, though there is some experimental evidence that suggests sulfur-containing compounds have been the main detoxifying drug in the case of poisoning. 17,18 Since thallium(I) shows marked similarities to that of potassium cation, 19 its interaction with nucleotides, the monomeric units of DNA and RNA, would be of major biochemical interest.This work deals with the study of thallium(I) complexes by AMP and the determination their stability constants in different solutions of methanol + water to show how the solvent and their mixtures with various dielectric constants affect the complexation.Recently, more attention has been paid to binary solvent mixtures in this field. 20-22 Solute-solvent interactions are much more complex in mixed solvent systems than in pure solvents, due to the possibility of preferential solvation by any of the solvents present in the mixtures. Moreover, the solvent-solvent interactions produced in solvent mixtures can affect the solutesolvent interactions and therefore they can also affect preferential solvations. 23At present, there are two more imp...

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ChemInform Abstract: Fluorinated Alcohols as Solvents for Diels‐Alder Reactions of Chiral Acrylates.

et al. 1993

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1993 stereochemistry stereochemistry (general, optical resolution) O 0030 -054Fluorinated Alcohols as Solvents for Diels-Alder Reactions of Chiral Acrylates.-A series of investigations reveals that fluorinated alcohols, i.e. CF3-CH2-OH and CF3-CHOH-CF3, increase both the rate and endo/exo selectivity of Diels-Alder reactions of cyclopentadiene with (-)-menthyl and (-)-8-phenylmenthyl acrylate. Furthermore, the diastereofacial selectivity in reactions with (-)-menthyl acrylate is increased as well in the presence of fluorinated alcohols. -(CATIVIELA, C.; GARCIA, J. I.; MAYORAL, J. A.; ROYO, A.

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Fluorinated alcohols as solvents for diels-alder reactions of chiral acrylates

Cited by 23 publications

References 16 publications

The Role of Menthyl Group in Catalyzed Asymmetric Diels−Alder Reactions. A Combined Quantum Mechanics/Molecular Mechanics Study

The Role of Menthyl Group in Catalyzed Asymmetric Diels−Alder Reactions. A Combined Quantum Mechanics/Molecular Mechanics Study

Complexation of Thallium(I) with Adenosine 5′-Monophosphate in Aqueous Methanol Solutions

ChemInform Abstract: Fluorinated Alcohols as Solvents for Diels‐Alder Reactions of Chiral Acrylates.

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