Highly diastereoselective allylic azide formation and isomerization. Synthesis of 3(2'-amino)-beta-lactams

The stereoselective anti SN2' attack of NaN3 to 3-alkenyl-3-bromo-azetidin-2-ones gave a mixture of diastereomeric azides in fast equilibrium. The [3,3]-sigmatropic rearrangement of allylic azides occurred with complete stereocontrol, allowing the equilibrium to be directed preferentially toward the (E)- or (Z)-isomer, useful precursors of 3(2'-amino)-beta-lactams. [reaction: see text]     

Compatti olomorficamente convessi di uno spazio analitico

Riassunto In questo lavoro si considerano sottoinsiemi compatti olomorficamente convessi di uno spazio analitico non ridotto e si prova che questi sono caratterizzati, come nel caso ridotto, dagli analoghi dei teoremiA eB di Cartan. Si dà inoltre una caratterizzazione di certi morfismi in un compatto olomorficamente convesso.

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Summary In this paper we consider compact holomorphically convex subsets of a non reduced analytic space and we prove that they are characterized, as in the reduced case, by the analogous of Cartan's theoremsA andB. We give also a characterization of some morphisms in a compact holomorphically convex set.

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Lavoro eseguito nell'ambito del G.N.S.A.G.A. del C.N.R.     

Convergence of Gauss type product formulas for the evaluation of two-dimensional Cauchy principal value integrals

The authors consider product rules of Gauss type for the numerical approximation of certain two-dimensional Cauchy principal value integrals with respect to generalized smooth Jacobi weight functions.Convergence results for these rules are given, and some asymptotic estimates of the remainder are established.Work sponsored by Italian Research Council and by the Ministero della Pubblica Istruzione of Italy.     

Oxidation of aqueous solutions of cobalt(II) in the presence of some aminoacids

Summary The complexes between cobalt(III) and aminoacids such as glutamine, asparagine, glutamic acid, aspartic acid and proline were studied.Cobalt(III)-aminoacid systems were investigated by spectrophotometry after oxidizing the cobalt(II) complexes by sodium peroxide. The variation of the absorption spectra shows the pH dependence of the process and it is clear that the formation of the complexes occurs through oxo-intermediates.Complexation ratios, molar absorptivity values and the concentration quotients at equilibrium were determined at pH 2.2 to avoid the formation of binuclear dioxygen-cobalt complexes.     

Photophysical properties and antibacterial activity of meso-substituted cationic porphyrins

A series of derivatives of 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphine, where one N-methyl group was replaced by a hydrocarbon chain ranging from C6 to C22, were characterized for their photophysical and photosensitizing properties. The absorption and fluorescence features of the various compounds in neutral aqueous solutions were typical of largely monomeric porphyrins, with the exception of the C22 derivative, which appeared to be extensively aggregated. This was confirmed by the very low triplet quantum yield and lifetime of the C22 derivative as compared with 0.2-0.7 quantum yields and 88-167 micros lifetimes for the other porphyrins. The photophysical properties and photosensitizing activity toward N-acetyl-L-tryptophanamide of the C22 porphyrin became comparable to those typical of the other derivatives in 2% aqueous sodium dodecyl sulfate, where the C22 compound is fully monomerized. All the porphyrin derivatives exhibited at micromolar concentrations photoinactivation activity against both Staphylococcus aureus and Escherichia coli, even though the gram-negative bacteria were markedly less photosensitive. The photosensitizing efficiency was influenced by (1) the amount of cell-bound porphyrin, which increased with increasing length of the hydrocarbon chain; and (2) the tendency to undergo partial aggregation in the cell, which seems to be especially important for the C22 derivative.     

Qualitative and Quantitative Evaluation of Some Vocal Function Parameters Following Fitting of a Prosthesis

The insertion of a prosthesis and restoration with pectoralis major myocutaneous flaps for patients subjected to total pharyngolaryngectomy is a technique now universally accepted; however the literature on the subject is lacking. Our study considers 10 patients subjected to total pharyngolaryngecto-my and restoration with pectoralis major myocutaneous flaps who were fitted with vocal function prostheses and a control group of 50 subjects treated with a total laryngectomy without pectoralis major myocutaneous flaps and who were fitted with vocal function prostheses. Specific qualitative and quantitative parameters were compared. The quantitative measurement of the levels of voice intensity and the evaluation of the harmonics-to-noise ratio were not statistically significant (p > 0.05) between the two study groups at either high- or low-volume speech. On the contrary, statistically significant differences were found (p < 0.05) for the basic frequency of both the low and the high volume voice. For the qualitative analysis seven parameters were established for evaluation by trained and untrained listeners; on the basis of these parameters the control group had statistically better voices.     

Lewis acid-mediated azidolysis of 2,3-three membered heterocyclic amines

The Lewis acid-catalyzed regioselective azidolysis of 2,3-three membered heterocyclic amines has been investigated. The results obtained demonstrated that using TMSN₃ as a source of azide, the appropriate choice of Lewis acid allowed to obtain different regio- and stereocontrolled precursors of aminoalcoholic and triaminic sequences. Considering the occurrence of these moieties in the structure of many biologically active compounds, the present methodologies could represent a powerful tool in organic synthesis for the preparation of interesting molecules.     

Design and synthesis of fluorescent galactolipid probes

Fluorescent galactolipid analogues (1, 1a, and 2) have been synthesized with a pyrene group attached to the amino-terminal of a hexanoyl chain bound to an otherwise normal galactolipid structure. The synthetic lipids are obtained from peracetyl galactose by a general and versatile procedure based on the trichloroacetimidate methodology. The intense violet fluorescence (376 and 395 nm) and good photostability of pyrene make these compounds highly suitable as probes to study galactolipid metabolism. As proof of concept, we report that compound 2 is a valid tool to detect galactolipase activity in enzymatic preparations of potato tubers.     

Reactions of Ru3(CO)12 with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru3(CO)9[μ3-η2-HC=N(CH2)3Si(OEt)3]

Ru₃(CO)₁₂ has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH₂], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH₂)CH₃] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)₃Si(CH₂)₃NCO] and the compound tb [(EtO)₃Si(CH₂)₃NHC(=O)OCH₂C≡CCH₂OC(=O)NH(CH₂)₃Si(OEt)₃] in hydrocarbon solution. Some reactions in CH₃OH/KOH solution (followed by acidification) have also been performed. The main products of the reactions with ene-ynes are the clusters Ru₃(CO)₆(μ-CO)₂L₂ (L = C₆H₈, C₇H₁₀) and their demolition products, the “ferrole” Ru₂(CO)₆L₂ complexes. One of the isomers of Ru₃(CO)₆(μ-CO)₂L₂, and Ru₂(CO)₆L₂ (L = C₇H₁₀) have been reacted with vinyl-triethoxysilane [(EtO)₃SiCH=CH₂]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization of vinyl-triethoxysilane occurred. The reactions of Ru₃(CO)₁₂ with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me₃NO) lead to the same products, that is the isomeric complexes (μ-H)Ru₃(CO)₉[C=N(H)(CH₂)₃Si(OEt)₃] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques. This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday.     

Formation of cobalt(III) compounds with some peptides

Summary The complexes formed from cobalt(III) and dipeptides such as glycylglycine, glycylaspartic acid, glycylthreonine, glycyltyrosine and glycylproline were studied. The formation process of cobalt(III)-dipeptide species was investigated by spectrophotometry after oxidizing the cobalt(II) complexes by sodium peroxide. The formation of the cobalt(III) complexes occurs through an oxo-intermediate, as shown by the spectral behaviour, and depends on the pH of the solutions.Complex stoichiometries, molar absorptivities and concentration ratios at the equilibrium of the cobalt(III)-dipeptide complexes were determined at pH 2.2 to avoid the formation of binuclear dioxygen-cobalt complexes.