Mild and effective cleavage of esters with bis(tributyltin) oxide: A useful application in the deprotection of Pom penicillanate esters

(Pivaloyloxy)methyl 6,6-dihalo-, 6-monosubstituted- and 6-halo 1,1-dioxide penicillanates, N-benzoylglycine methyl ester and several selected esters are efficiently hydrolyzed with bis(tributyltin) oxide (nBu₃Sn)₂O with yields from 43 to 100%.     

Development of Luminescent Terbium(III) Chelates for Protein Labelling: Effect of triplet-state energy level

The synthesis of novel Tb^III labels suitable for protein labelling are reported. Their luminescence properties as antibody conjugates were measured and compared to the results of corresponding Tb^III chelates of the parent ligand structures. When the lowest triplet-state energy level of the parent donor ligand was over 23000 cm^?1, i.e., the energy gap between the ⁵D₄ level of Tb^III and the lowest triplet-state energy level of the ligand exceeded 2600 cm^?1, the label derivative with a long decay time (τ = 1.35–2.93 ms) and a high luminescence yield (?. Φ = 3770–4560) was found to be suitable for bioaffinity assays.     

Fragmentation of carbohydrate anomeric alkoxyl radicals. A new synthesis of chiral beta-iodo azides, vinyl azides, and 2H-azirines

[reaction: see text] The reaction of 3-azido-2,3-dideoxy-hexopyranose compounds from the d-gluco, d-galacto, d-lacto, and l-arabino carbohydrate series, with (diacetoxyiodo)benzene and iodine, generated 2-azido-1,2-dideoxy-1-iodo-alditols with one carbon less than the starting carbohydrate. These beta-iodo azides could be transformed by dehydroiodination into vinyl azides, which in turn afforded 3-monosubstituted 2H-azirines under thermal conditions. These beta-iodo azides and 2H-azirines may be interesting chiral synthons for the preparation of more complex heterocyclic systems.     

Facile synthesis of new fullerene-Ru(bpy)3 dyads bearing phosphonate groups for hybrid organic-inorganic materials

Fullerene reacted with mono- and diphosphonate-bearing bipyridines by way of Bingel-type reactions to give adducts which were easily transformed in the corresponding dyads by forming Ru(bpy)₃ complexes. Electrochemical measurements and the observation of heavy quenching of the Ru(bpy)₃ luminescence manifested strong interactions between the active moieties. Attempts to include the dyads into inorganic matrices derived from zirconium phosphate are reported.     

Pyridazines. Part 31: synthesis and antiplatelet activity of 4,5-disubstituted-6-phenyl-3(2H)-pyridazinones

This paper describes the synthesis and the antiplatelet activity of a series of 4,5-disubstituted-6-phenyl-3(2H)-pyridazinones. Some of these compounds show a dose-dependent activity and were found to be more active than their 5-substituted analogues.     

Synthesis and aldol reactivity of o- and C-enolate complexes of nickel

The often facile C-/O-tautomerization of transition metal enolates is severely hindered in the cyclic Ni complexes 1 and 2, allowing the study of their individual reactivities. At room temperature only the O-bound tautomer, 2, reacts with aldehydes, giving rise to the corresponding addition products.     

Synthesis of alpha-acyl-functionalized azacycles by Pd-catalyzed cross-coupling reactions of alpha-alkoxyboronates with lactam-derived vinyl triflates

Alkoxydienyl- and alkoxystyrylboronates were used for Pd-catalyzed cross-coupling reactions with lactam-derived vinyl triflates. The hydrolysis of the coupling products with alkoxystyrylboronates provided the corresponding alpha-acyl-substituted 3,4-dihydro-(2H)-pyridines and 2,3,4,5-tetrahydroazepines in good to high yields. The hydrolysis of the coupling products with alkoxydienylboronates, performed in the presence of Amberlyst 15, resulted in a Nazarov-type cyclization that afforded hexahydro[1]pyrindin-7-ones and 3,4,5,6,7,8-hexahydro-(2H)-cyclopenta[b]azepin-8-ones. This methodology represents a novel and efficient procedure for the preparation of these classes of azacyclic compounds.     

Supramolecular Assembling of Complex Tellurium Salts: Synthesis and Crystal Structures of {Cs[PhTeCl4]·CH3OH} and Cs[PhTeBr4]

The direct reaction between PhTeCl₃ and CsCl in methanol affords {Cs[PhTeCl₄]·CH₃OH}. Cs[PhTeBr₄] was prepared by refluxing [2‐Br‐C₅NH₅][PhTeBr₄] and CsCl in ethanol in the presence of an excess of HBr. In {Cs[PhTeCl₄]·CH₃OH} the [PhTeCl₄]^— units form dimers by secondary Te···Cl bonds with methanol molecules bridging adjacent Cs⁺ cations. In both compounds, the alkali metal cation interacts secondarily with the chlorine and bromine Te‐ligands, achieving singular coordination polyhedrons and holding the lattices in supramolecular tridimensional assemblies. The new complexes, {Cs[PhTeCl₄]·CH₃OH} and Cs[PhTeBr₄], crystallize in the space groups P2₁/c and P2₁/n, respectively. Only one such structure has been reported before.     

Fragmentation of carbohydrate anomeric alkoxyl radicals: a new synthesis of 1,1-difluoro-1-iodo alditols

[reaction: see text]. The beta-fragmentation of 2,2-difluoro-saccharide anomeric alkoxyl radicals, generated under oxidative condition by treatment of the respective alcohols with (diacetoxyiodo)benzene (DIB) and iodine, afforded 1,1-difluoro-1-iodo alditols in high yield. The reactivity of the fluorinated radical generated by rupture of the C-I bond has been preliminarily assessed by reductive deiodination with tributyltin hydride/AIBN and intermolecular allylation using the Keck reaction.     

CO2 poisoning effect on HY zeolite dehydration catalyst

The poisoning effect of CO₂ on a HY catalyst for the dehydration of 2-(2-hydroxyethyl)-pyridine (HEP) to 2-vinylpyridine (VP) has been investigated by FT-IR analysis in the presence and absence of pyridine. CO₂ was found to adsorb on sites not occupied by pyridine,i.e. on weak basic sites accompanying the strongly acidic sites, characteristic of Y zeolites in the protonated form. When the basic sites are occupied by preadsorbed CO₂, HEP dehydration cannot take place any more through the minor mechanism, involving a couple of acid-base sites, and the reaction proceeds only through the major mechanism, involving a carbocation intermediate, on Br?nsted acid sites only.