Iodocyclization/base-induced hydrodeiodination reaction of 5-substituted 4-alkenols. The influence of substituent on the stereoselective pathway

The electrophilic iodocyclization reaction of (Z)- and (E)-5-n-alkylsubstituted 4-alken-1-ols followed by base-induced hydrodeiodination reaction stereoselectively gave, respectively, (Z)- and (E)-alkylidentetrahydrofurans in high yield. Completely different outcomes were observed with (Z)- and (E)-6,6-dimethylhept-4-en-1-ol: their iodocyclization furnished, respectively, threo- and erythro-2-(1-iodo-2,2-dimetylpropyl)tetrahydrofuran with high stereoselectivity. The threo isomer gave clean formation of 6-tert-butyl-3,4-dihydro-2H-pyran by base-induced ring expansion, while erythro isomer underwent a base-induced ring contraction to 1-cyclopropyl-3,3-dimethylbutan-1-one. Moreover, (Z)- and (E)-5-cyclopropylpent-4-en-1-ol underwent a 6-endo-iodocyclization to threo- and erythro-2-cyclopropyl-3-iodotetrahydro-2H-pyran, respectively, that under the same basic treatment, gave two isomeric 6-cyclopropyldihydro-2H-pyrans in a stereoselective fashion.     

Methyl and silyl mesolytic dissociations in the radical cations and radical anions of but-1-ene,allylsilane, hexa-1,3-diene,and penta-2,4-dienylsilane. CAS-MCSCF and coupled cluster theoretical study

Methyl or silyl dissociation in the CH(2)=CHCH(2)-XH(3) (a-XH(3)(*)(+)) and CH(2)=CHCH=CHCH(2)-XH(3) (p-XH(3)(*) (+)) radical cations (X = C, Si) yields a(+) or p(+) and XH(3)(*). Similarly, the radical anions a-CH(3)(*) (-) and p-CH(3)(*) (-) give the pi-delocalized anion and CH(3)(*) preferentially. In contrast, a-SiH(3)(*) (-) and p-SiH(3)(*-) prefer to dissociate into the pi-delocalized radical and silide. All reactions are endoergic: by 43-50 kcal mol(-)(1) in the radical cations, and easier to some extent in the radical anions, that require 29-33 (X = C) and 13-14 kcal mol(-)(1) (X = Si). The fragmentation energy profiles do not present significant barriers for the backward process in the case of the radical cations. All radical anions exhibit an energy maximum along the dissociation pathway, but the barrier is lower than the dissociation limit. Fragmentation is "activated" more in the anions than in the cations with respect to homolysis in the corresponding neutrals (that requires 72-81 kcal mol(-)(1)). Wave function analysis indicates that the C-X bond cleavage in the hydrocarbon radical ions, although formally comparable to a homolytic process, is at variance with this model, due to the spin recoupling of one of the two C-X bond electrons with the originally unpaired electron. This is basically true also for the silyl-substituted radical anions, in which the initial more delocalized charge distribution might suggest some heterolytic character of the bond cleavage.     

Crystalline polysilicate magadiite with intercalated n-alkylmonoamine and some correlations involving thermochemical data

Synthesized hydrated lamellar acidic crystalline magadiite (H₂Si₁₄O₂₉·2H₂O) nanocompound was used as host for intercalation of polar n-alkylmonoamine molecules of the general formula H₃C(CH₂)_nNH₂ (n = 1–6) in aqueous solution. The original interlayer distance (d) of 1500 pm, determined by X-ray powder diffraction patterns, increases after intercalation. The values correlated with the number of aliphatic amine carbon (n_c) atoms: d = [(1312 ± 11) + (21 ± 2)]n_c. The amount of intercalated amines (N_s), decreased as n_c increased: N_s = [(5.82 ± 0.04) − (0.45 ± 0.01)]n_c. The acidic layered nanocompound was calorimetrically titrated with the amines and the thermodynamic data gave exothermic values for all guest molecules, as shown by the correlation: Δ_intH = −[(24.45 ± 0.49) − (1.91 ± 0.10)]n_c and d = [(1576 ± 16) − (10.8 ± 1.0)]Δ_intH. The negative values of the Gibbs energies and the positive entropies also presented the correlations: Δ_intG = −[(22.8 ± 0.2) − (0.2 ± 0.1)]n_c and Δ_intS = [(6 ± 1) + (5 ± 1)]n_c, respectively.     

A unique tautomer of 1‐n‐hexyl‐3‐phenyl‐1H‐pyrazol‐5‐ol

In the title compound, C₁₅H₂₀N₂O, the bond distances and angles are consistent with the presence of the hydroxy tautomer. This tautomer was unambiguously determined by the clear presence of a H atom bonded to oxygen, as well as the total absence of any residual electron density around the N atom in the heterocycle, thus precluding any possibility of desmotropism.     

Characterization of the 310-helix in model peptides by HRMAS NMR spectroscopy

A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis.     

SOME PRELIMINARY INFORMATION ON SYNDIOTACTIC POLYSTYRENE CATALYSTS

Syndiotactic specific polymerization of styrene has been investigated by ~(13)C NMR analysis and isotopic laelling methods. The value of the activation energy involved in the steric control has been determined. Some information of the number of the active sites and on the life of the catalysts is reported.     

Facile and practical enantioselective synthesis of propargylic alcohols by direct addition of alkynes to aldehydes catalyzed by chiral disulfide–oxazolidine ligands

The enantioselective alkynylation reaction of aldehydes with alkynes and diethylzinc, catalyzed by chiral disulfide–oxazolidine ligands, provides a simple, practical and inexpensive method to access chiral propargylic alcohols in good yields and satisfactory ee's.     

Crystalline calcium phenylphosphonate—thermodynamic data on n-alkylmonoamine intercalations

Lamellar crystalline calcium phenylphosphonate, as anhydrous Ca(HO₃PC₆H₅)₂ and hydrated Ca(HO₃PC₆H₅)₂·2H₂O compounds, were used as hosts for intercalation of polar n-alkylmonoamine molecules of the general formula CH₃(CH₂)_nNH₂ (n=0–4, 7) in water or 1,2-dichloroethane. An increase in the interlayer distance was observed. The exothermic enthalpic values for intercalation increased with the number of carbon atoms and with increasing concentration of the amines. The intercalation followed by a titration procedure in the solid/liquid interface with Ca(HO₃PC₆H₅)₂·2H₂O and Ca(HO₃PC₆H₅)₂ gave the enthalpy/number of carbons correlations: Δ_intH=−(1.74±0.43)–(1.30±0.13)n_c and Δ_intH=−(4.15±0.15)–(1.07±0.03)n_c, for water and 1,2-dichloroethane, respectively. A similar correlation Δ_intH=−(4.27±0.80)–(1.85±0.21)n_c was obtained in water by using the ampoule breaking procedure for Ca(HO₃PC₆H₅)₂·2H₂O. The increase in exothermic enthalpic values with the increase in n-aliphatic carbon atoms is more pronounced for the anhydrous compound and also when using the ampoule breaking procedure. The Gibbs free energies are negative. Positive entropic values favor intercalation in these systems.     

Quantum logics seen as quantum testability theories

We confute logical relativism and forward an alternative epistemological thesis according to which nonstandard truth-theories are considered theories of some metalinguistic concepts which do not coincide with truth, this latter concept being exhaustively described by Tarski's truth theory. We illustrate our viewpoint by showing that quantum logics can be interpreted as quantum physical theories of the metalinguistic concept of testability in the framework of a suitable classical language (with Tarskian semantics).