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PubMed1988

The actions of cyclopentane analogues of glutamic acid at binding sites for kainic and glutamic acids.

The actions of the four isomers of 1-amino-1, 3-cyclopentane dicarboxylate (ACPD), a conformationally restricted analogue of glutamate, have been examined for their ability to displace radiolabelled kainate and glutamate from their binding sites on membranes prepared from rat brain. All four of the isomers reduced specific kainate binding, and all enhanced that of glutamate although one (D-(-)-cis-(1R,3R)-ACPD) was significantly more active in this respect than were the other three. The results are discussed in terms of the pharmacological effects of the isomers of ACPD on single neurones and the possible structural requirements of the NMDA and kainate receptors.

Amino Acids↗
PubMed1986

Structure-activity studies on the activity of a series of cyclopentane GABA analogues on GABAA receptors and GABA uptake.

A series of analogues of gamma-aminobutyric acid (GABA) has been investigated for GABA mimetic activity on the isolated guinea-pig ileum, facilitation of [3H]diazepam binding in rat brain membranes and inhibition of [3H]GABA uptake from rat brain cortical slices. The derivatives tested include six racemic amino acids, all of which contain a 'GABA backbone' with the conformation restricted by a cyclopentane or cyclopentene ring system. From the more potent analogues, five optically pure compounds, including (+)-(4S)-4-aminocyclopent-1-ene-1-carboxylic acid and its (-)-4R enantiomer, have also been assessed as GABA agonists. Of the racemic analogues, 4-aminocyclopent-1-ene-1-carboxylic acid and trans-3-aminocyclopentane-1-carboxylic acid were the most potent at GABAA receptors, while most of the analogues had considerable activity on GABA uptake. The individual resolved isomers of 4-aminocyclopent-1-ene-carboxylic acid and of trans-3-aminocyclopentane-1-carboxylic acid displayed great specificity for GABA receptor and GABA uptake sites. For example (+)-(4S)-4-aminocyclopent-1-ene-1-carboxylic acid was approximately twice as potent as GABA and about 600 times more active than the (-)-4R isomer on the guinea-pig ileum, while it was not significantly active as a GABA uptake inhibitor at 500 microM. On the other hand, its (-)-4R isomer was selective for inhibiting GABA uptake with an IC50 equal to that of racemic nipecotic acid.

Animals↗
PubMed1989

Effect of alterations in the cyclopentane ring on bone resorptive activity of prostaglandin.

Previous studies have shown that the natural prostanoids, PGE2, PGE1 and PGF2 alpha are potent stimulators of bone resorption. In this study, we have examined the effects of alterations in the cyclopentane ring of these prostanoids for their effect on the resorptive response of cultured long bones from 19-day fetal rats as measured by the release of previously incorporated 45Ca. Indomethacin (10(-6)M) was added to minimize endogenous prostaglandin production. In this system PGE2 and PGE1, the 9 keto, 11 alpha hydroxy compounds, were approximately equally effective at concentrations of 10(-8) to 10(-6) M. The 9 alpha hydroxy, 11 alpha hydroxy compound, PGF2 alpha, was active at 10(-7) to 10(-5) M. In contrast, the 9 alpha hydroxy, 11-keto compound, PGD2, showed only a minimal stimulation of bone resorption at 10(-5) M. While these data suggested that the 11 alpha hydroxy group was important for bone resorbing activity, 11 beta PGE2 and 11-deoxy PGE1 were only slightly less potent than their physiologic counterparts. Both 9 beta, 11 alpha PGF2 and 9 alpha, 11 beta PGF2 were less potent than PGF2 alpha but did cause substantial stimulation of bone resorption and were equally effective at 10(-6) to 10(-5) M. 9 alpha, 11 beta PGF2 alpha is of particular interest since it is major metabolite of PGD2. These results suggest that the binding of prostanoids to the receptor which mediates bone resorption is affected by changes at the 9 and 11 positions of the pentane ring but do not support the hypothesis that the 11 alpha OH function is essential for this biological activity.

Animals↗
PubMed1996

Differential effects of learning and recall of a spatial task on phosphoinositide hydrolysis induced by the metabotropic glutamate receptor agonist 1S,3R-ACPD (1S,3R-1-amino-cyclopentane-1,3-discarboxylic acid) in the hippocampus and the prefrontal cortex of rats.

Phosphoinositide (PI) hydrolysis, stimulated by 1S,3R-1-amino-cyclopentane-1,3-dicarboxylic acid (1S,3R-ACPD), an agonist of metabotropic glutamate receptors (mGluRs), was measured in hippocampal and prefrontal cortical slices obtained from rats which had been trained for 8 days in a Morris water maze and had learned an allocentric spatial task. Brain slices were pre-labeled with myo-3H-inositol and 1S,3R-ACPD (100 microM) stimulation was assessed by measuring the accumulation of [3H]inositol phosphates ([3H]IPs) in the presence of Li+. Measurements conducted 24 h following the last training session revealed no differences in 1S,3R-ACPD-stimulated formation of [3H]IPs, either in the hippocampus or in the prefrontal cortex. However, a diminished response to mGluRs stimulation was detected in the hippocampus of animals re-trained after an 11-day interval. The decrease was not evident in the prefrontal cortex. These data indicate a differential involvement of the hippocampus and the prefrontal cortex in the processing of spatial information and correspond to the functional differences attributed to these areas.

Animals↗
PubMed2002

Synthesis and pharmacology of 3-hydroxy-delta2-isoxazoline-cyclopentane analogues of glutamic acid.

The synthesis and pharmacology of two potential glutamic acid receptor ligands are described. Preparation of the bicyclic 3-hydroxy-delta2-isoxazoline-cyclopentane derivatives (+/-)-7 and (+/-)-8 was accomplished via 1,3-dipolar cycloaddition of bromonitrile oxide to suitably protected 1-amino-cyclopent-3-enecarboxylic acids. Their structure was established using a combination of 1H NMR spectroscopy and molecular mechanics calculations carried out on the intermediate cycloadducts (+/-)-11 and (+/-)-12. Amino acid derivatives (+/-)-7 and (+/-)-8 were assayed at ionotropic and metabotropic glutamic acid receptor subtypes and their activity compared with that of trans-ACPD and cis-ACPD. The results show that the replacement of the omega-carboxylic group of the model compounds with the 3-hydroxy-delta2-isoxazoline moiety abolishes or reduces drastically the activity at the metabotropic glutamate receptors. Conversely, on passing from cis-ACPD to derivative (+/-)-8, the agonist activity at NMDA receptors is almost unaffected.

Amino Acids↗
PubMed1998

Plasticity of Cl-Te-Cl Fragments. Synthesis, Single-Crystal X-ray, and NBO Study of (1-Thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-Trichloride.

Tellurium tetrachloride and allylphenyl sulfide react to form (1-thia-2-tellura-1-phenyl-4-chloro)cyclopentane 2,2,2-trichloride. The crystal and molecular structure were determined by single-crystal X-ray techniques. The crystals belong to the monoclinic system, space group P2(1)/c (No. 14) with a = 6.020(3) Å, b = 11.46(1) Å, c = 20.156(2) Å, beta = 97.53(2) degrees, V = 1379(1) Å(3), and Z = 4. The structure was refined to the final R value of 0.036. The coordination around Te(IV) is distorted psi octahedral with three Cl atoms in the equatorial positions. The axial Te(1)-C(1) bond opposite to the lone pair of electrons at the Te(IV) atom completes the coordination polyhedron. The intramolecular Te-S distance is 2.903(3) Å. Symmetric and asymmetric deformation modes were established to describe the plasticity of the Cl-Te-Cl fragments extracted from the Cambridge Structural Database. The hypervalency of Te(IV) manifests itself as plasticity in the equatorial plane of the coordination sphere. The NBO calculations show that all of the equatorial Te-Cl bonds are highly polarized and the electrons reside mainly on the Cl atoms.

Journal Article↗
PubMed2000

Steric influence of E- or Z-monosubstituted and terminally disubstituted vinyl groups in matrix-isolated cyclopentane-1,3-diyl triplet diradicals as probed by the zero-field EPR D parameter

The zero-field D parameter of the localized E, Z, and disubstituted vinyl cyclopentane-1,3-diyl triplet diradicals V was determined at 77 K in a 2-methyltetrahydrofuran (2-MTHF) matrix. Good linear correlations were obtained with the semiempirically (PM3; r(2) = 0. 991, n = 19) and DFT (B3LYP; r(2) = 0.998, n = 7) calculated spin densities of the triplet diradicals. The D values for the disubstituted triplet diradicals V are generally larger than the corresponding monosubstituted ones and, thus, the former are less well-delocalized and thereby more poorly stabilized. For the E- and Z-diastereomeric pairs V, only marginal changes in the theoretical assessed spin densities as well as in the D values have been found. Steric effects operate and distort the conformation of the vinyl substituent in the triplet diradical V. This is adequately reproduced by theoretical calculations. For the diphenyl-substituted triplet diradical Vl, for example, they show a more or less planar alignment of the E-phenyl group and the allylic pi system (torsion angle 12 degrees ) and thus optimal delocalization of spin, whereas the Z-phenyl group is twisted about 78 degrees out of plane and therefore is not involved in the delocalization and stabilization of spin. This results in a slightly higher D value (0.0368 cm(-)(1)), and the spin is delocalized less than in the monosubstituted E-Vm one (0.0357 cm(-)(1)).

Journal Article↗
PubMed2000

Wavelength-selective photodenitrogenation of azoalkanes to high-spin polyradicals with cyclopentane-1,3-diyl spin-carrying units and their photobleaching: EPR/UV spectroscopy and product studies of the matrix-isolated species.

The photolysis of the mono-, bis-, and trisazoalkanes 1, 2, and 3 in a toluene matrix at 77 K has been studied by EPR and UV spectroscopy. The purpose was to find the optimal conditions for the generation of the corresponding organic high-spin polyradicals (the triplet diradicals D-1, D-2, and D-3, the tetraradicals T-2 and T-3, and the hexaradical H-3) all with localized cyclopentane-1,3-diyl spin-carrying units, connected by m-phenylene (except D-1) as ferromagnetic coupler. Irradiation of these azoalkanes at 333, 351, or 364 nm gave different polyradical compositions. This observed wavelength dependence is due to the secondary photoreaction (photobleaching) of the polyradical intermediate. The photobleaching process has been examined in detail for the triplet diradical D-1, for which pi,pi excitation affords the cyclopentenes 5 instead of the housane 4 (the usual product of the diradical D-1 on warm-up of the matrix). The pi,pi-excited diradical D-1 fragments into a pair of allyl and methyl radicals (the latter was observed by EPR spectroscopy of a photobleached sample), and recombination affords the cyclopentene. Similar photochemical events are proposed for the photobleaching of the tetraradical T-2 and hexaradical H-3, derived from the respective azoalkanes 2 and 3. Thus, photobleaching of the polyradicals competes effectively with their photogeneration from the azoalkane. This unavoidable event is the consequence of spectral overlap between the cumyl-radical pi,pi chromophore of the polyradical and the n,pi chromophore of the azoalkane at the wavelength (364 nm), at which the latter is photoactive for the required extrusion of molecular nitrogen.

Journal Article↗
PubMed2004

Theoretical calculations of the effects of 2-heavier group 14 element and substituents on the singlet-triplet energy gap in cyclopentane-1,3-diyls and computational prediction of the reactivity of singlet 2-silacyclopentane-1,3-diyls.

UDFT and CASSCF calculations with the 6-31G(d) basis set were performed to investigate the heavier group 14 element (M) effect on the ground-state spin multiplicity of cyclopentane-1,3-diyls and their reactivity. The calculations find that 2-metallacyclopentane-1,3-diyls (M = Si, Ge) that possess a variety of substituents (X = H, Me, F, OR, SiH(3)) at M(2) are singlet ground-state molecules. The energies of the 1,3-diphenyl-substituted singlet 2-silacyclopentane-1,3-diyls are calculated to be ca. 5 kcal/mol lower than those of the intramolecular ring-closure products, i.e., 1,4-diphenyl-5-silabicyclo[2.1.0]pentanes, at the B3LYP/6-31G(d) level of theory. The energy barrier for the disrotatory ring closure of singlet 2,2-dimethyl-1,3-diphenyl-2-silacyclopentane-1,3-diyl (lambda(calcd) = 757 nm, f = 1.01 at RCIS/6-31G(d)) to the corresponding 5-silabicyclo[2.1.0]pentane is computed to be 11.6 kcal/mol, which is 13.1 kcal/mol lower in energy than that for the conrotatory ring-opening to a 3-silapenta-1,4-diene. The computational work predicts that singlet 1,3-diaryl-2-silacyclopentane-1,3-diyls are persistent molecules under conditions without trapping agents.

Journal Article↗
PubMed1997

Conformation of a Geminal Dicyclopropyl-Substituted Trimethylenemethane Triplet [2-(Dicyclopropylmethylidene)cyclopentane-1,3-diyl].

Triplet 2-(dicyclopropylmethylidene)cyclopentane-1,3-diyl, CP2TMM, has a Deltam(s) = 2 ESR transition revealing hyperfine splitting consistent with coupling to two equivalent alpha hydrogens and five equivalent beta hydrogens and one other hydrogen with a small hyperfine coupling constant. This is consistent only with a conformation in which one cyclopropane ring conjugates with the pi triplet so that the other cyclopropane is twisted allowing the tertiary cyclopropyl hydrogen to hyperconjugate. Geometry optimization of the triplet state of CP2TMM was carried out using the 3-21G basis set with a UHF wave function and while the singlet state was optimized using a GVB perfect pairing wave function. The most stable conformation of each spin state is a C(2)-symmetric structure providing a 10 kcal/mol singlet-triplet energy gap favoring the triplet. This gap is reproduced at the 6-31G level using the 3-21G geometries. However, this structure cannot reproduce the hyperfine splitting observed; 1 kcal/mol higher in energy is an asymmetrical conformation of triplet CP2TMM which can account for the hyperfine interactions.

Journal Article↗
PubMed1999

The EPR-Spectral D Parameter of Photochemically Generated Cyclopentane-1,3-diyl Triplet Diradicals as a Quantitative Measure of Spin Delocalization in Vinyl-, Phenyl-, and Carbonyl-Substituted Radicals.

The zero-field splitting parameter D of the localized cyclopentane-1,3-diyl triplet diradicals T, generated in a 2-methyltetrahydrofuran (MTHF) glass matrix at 77 K through photochemical deazetation of the corresponding azoalkanes 1-13, has been determined by EPR spectroscopy. It is demonstrated that the D parameter reliably reflects the changes caused by the alkyl (simple and oxyfunctionalized), vinyl, and carbonyl substituents of the spin densities at the radical site. Thus, spin delocalization of the substituents and stabilization of the radical center follow the order vinyl > phenyl > carbonyl >> alkyl. This trend is confirmed by the excellent linear correlations with the reported alpha-hyperfine coupling constants (alpha-hfc) of the corresponding monoradicals and computed semiempirical (PM3 method) spin densities of the radical fragments M.

Journal Article↗
PubMed1999

Iridoids from Carbohydrates via Pauson-Khand Reaction: Synthesis of Advanced Highly Oxygenated Cyclopentane-Annulated Pyranosides from D-Glucal Derivatives.

The Pauson-Khand reaction on suitable 4-oxa-hept-1-en-6-ynes (1, 17) obtained from 3,4,6-tri-O-acetyl-D-glucal gives the cyclopentane-annulated pyranosides (2, 18) that can be efficiently and stereoselectivelly transformed into chiral, advanced, highly oxygenated intermediates (10, 16, 24) for the synthesis of iridoid aglycones.

Journal Article↗
PubMed2006

Thermal chemistry of 1-methyl-1-cyclopentene and methylene cyclopentane on Pt(111) surfaces: evidence for double-bond isomerization.

The thermal chemistry of 1-methyl-1-cyclopentene (1MCp(=)) and methylene cyclopentane (MeCp) was investigated on clean and hydrogen- and deuterium-predosed Pt(111) single-crystal surfaces by temperature-programmed desorption and reflection-absorption infrared spectroscopy. It was found that MeCp isomerizes easily to 1MCp(=) but that the reverse reaction does not occur, at least under our experimental conditions. The MeCp to 1MCp(=) isomerization is aided by the presence of coadsorbed hydrogen, and occurs through the formation of a common 1-methyl-1-cyclopentyl (1MCp-Pt) surface intermediate; that intermediate then undergoes beta-hydride elimination selectively at the ring position to form the 1MCp(=) product. In addition to this isomerization, both 1MCp(=) and MeCp also dehydrogenate on the Pt(111) surface to form a methylcyclopentadiene species, at 325 and 350 K, respectively. A small amount of benzene desorption is detected above 500 K with both reactants, indicative of a ring enlargement reaction. No evidence for the activation of any of the allylic hydrogens was obtained in either molecule.

Journal Article↗
PubMed2004

The outer valance orbital electron densities of cyclopentane by binary (e,2e) spectroscopy.

The binding energy spectra and electron distributions in momentum space of the valence orbitals of cyclopentane (C(5)H(10)) are studied by Electron Momentum Spectroscopy (EMS) in a noncoplanar symmetric geometry. The impact energy was 1200 eV plus binding energy and energy resolution of the EMS spectrometer was 1.2 eV. The experimental momentum profiles of the outer valence orbitals are compared with the theoretical momentum distributions calculated using Hartree-Fock and density functional theory (DFT) methods. The shapes of the experimental momentum distributions are generally quite well described by both the Hartree-Fock and DFT calculations when the large and diffuse basis sets are used.

Journal Article↗
PubMed1991

Excitatory Actions of the Metabotropic Excitatory Amino Acid Receptor Agonist, trans-(+/-)-1-amino-cyclopentane-1,3-dicarboxylate (t-ACPD), on Rat Thalamic Neurons In Vivo.

The metabotropic excitatory amino acid receptor agonist trans-(+/-)-1-amino-cyclopentane-1,3-dicarboxylate (t-ACPD) was applied to rat ventrobasal thalamic neurons by iontophoresis. This agonist typically evoked an excitatory response which was slower in onset and of longer duration than responses to the other excitatory amino acid agonists, N-methyl-aspartate, kainate or (R,S)-alpha-amino-3-hydroxy-5-methyl-4-isoxazolepropionate. Responses to t-ACPD were resistant to the excitatory amino acid antagonists 6-cyano-7-nitroquinoxaline-2,3-dione, 3-((RS)-2-carboxypiperazin-4-yl)-propyl-1-phosphonic acid and kynurenate. These results suggest that t-ACPD may exert its effects via the so-called 'metabotropic' excitatory amino acid receptor. The putative antagonists at this receptor, d-2-amino-4-phosphono-butyrate (d-AP4), l-2-amino-4-phosphono-butyrate (l-AP4) and l-2-amino-3-phosphono-propionate (l-AP3), were able to reduce responses to t-ACPD under certain circumstances. However, such antagonism was always accompanied by similar reductions in excitatory responses to other agonists. These non-selective effects would appear to limit the usefulness of AP4 and AP3 as antagonists of t-ACPD.

Journal Article↗