Maria Funicello

Stable five-coordinate [Pt(N Nt')(olefin)(R)X] complexes formed by oxidative addition to [Pt(N N′)(olefin)] precursors

Abstract The oxidative addition of an electrophilic reagent such as a halogen or an alkyl halide to a suitable three-coordinate species of the type [Pr( N N ′)(olefin)]( N N ′ = chelating N,N-ligand) affords a five-coordinate product. The reaction provides a new versatile route to the synthesis of trigonal bipyramidal complexes of general formula [Pt(X)(Y) N N ′)(olefin)] (X = halide; Y = hydrocarbyl or halide). This is apparently the first widely applicable oxidative addition process to three-coordinate M(0) organometallic derivatives of group 10 elements to give isolable five-coordinate M(II) products. Some general features of the addition and preliminary observations on the reaction mechanism are described.

Novel N-(2-benzo[b]thienyl)iminophosphoranes and their use in the synthesis of benzo[b]thieno[2,3-b]pyridines

Novel N-(2-benzo[b]thienyl)iminophosphoranes react with α,β-unsaturated aldehydes and ketones to give benzo[b]thieno[2,3-b]pyridines in an aza-Wittig/electrocyclic-ring closure process. The diphenylmethyliminophosphorane reacts with aromatic and heteroaromatic aldehydes to give iminic products: upon UV irradiation, two imines furnish cyclization products in acceptable yields.

Smiles rearrangement for the synthesis of 5-amino-substituted [1]benzothieno[2,3-b]pyridine

The Smiles rearrangement was successfully applied to 4-hydroxybenzo[b]thiophene furnishing a facile entry to the 4-amino derivative. The rearrangement was extended to 5-methoxy-4-methoxycarbonyl[1]benzothieno[2,3-b]pyridine obtained via aza-Wittig/electrocyclization reaction of novel N-(4-methoxybenzothiophen-2-yl)iminomethyldiphenylphosphorane with methyl trans-4-oxo-2-pentenoate. The preparation of a novel 5-amino-4-methoxycarbonyl[1]benzothieno[2,3-b]pyridine, which is of interest as a potential secondary peptide structure mimic, was successfully achieved.

Novel chiral calix[4]arenes by direct asymmetric epoxidation reaction.

We report the first asymmetric synthesis of trans optically active (+) C 2 1,3-bisarylepoxide of calix[4]arene in excellent chemical yield and >99% ee, and its enantiospecific conversion to the corresponding bis-dioxolane.

Facile Entry to 4‐ and 5‐Hydroxybenzofuran and to Their Amino Derivatives

Abstract An innovative one‐step procedure for the synthesis of 4‐hydroxybenzofuran and an improved synthesis of 5‐hydroxybenzofuran is reported. Such compounds were also transformed into their amino derivatives via Smiles rearrangement with good to high overall yields.

N-(3-Benzo[b]thienyl)iminophosphoranes toward the Synthesis of Benzo[b]thieno[3,2-b]pyridines: Reactivity and Alternative Regioselectivity with α,β-unsaturated Ketones and Aldehydes

Abstract The novel N-(3-benzo[b]thienyl)iminophosphoranes 1b–d react with α,β-unsaturated aldehydes and ketones 2a–e to give varying mixtures of the regioisomeric benzothieno[3,2-b]pyridines 3a–d and 4a–d as a result of preferential attack of either imino nitrogen or α-thienyl carbon at the enone carbonyl group. The findings indicate that the progressive replacement of phenyl with methyl P-substituent greatly enhances the reactivity of the phosphorane 1 and concomitantly enhances the propensity of the phosphorane itself for addition to the enone by the α-thienyl carbon.

Synthesis of new thienyl ring containing HIV-1 protease inhibitors: promising preliminary pharmacological evaluation against recombinant HIV-1 proteases.

A series of new thienyl ring containing analogues of nelfinavir and saquinavir with different substitution patterns were synthesized from suitable enantiopure diols. Their inhibitory activity against wild type recombinant HIV-1 protease was evaluated. In general thienyl groups spaced from the core by a methylene group gave products showing IC(50) in the nanomolar range, irrespective of the type and the substitution pattern of the heterocycle. The range of activity of the two most active compounds is substantially maintained or even increased against two commonly selected mutants, under drug pressure, such as V32I and V82A.

Ring opening of 2,3-epoxy 1-tosylates to halohydrins and subsequent elaboration to asymmetrical alcohols

Abstract 2,3 -epoxy alcohols-1-tosylates are regio and chemoselectively opened to the corresponding 3-halohydrins (I, Br, Cl): the reduction of the iodohydrins to the monoprotected diols and subsequent standard coupling of the tosyl group leads to a straightforward synthesis of optically active naturally occurring pheromones.

Heterocycles in peptidomimetics and pseudopeptides: design and synthesis.

This minireview provides a brief outline of the peculiar aspects of the preparation of peptidomimetic and pseudopeptidic structures containing heterocycles. In particular novel tricyclic structures are investigated as potential drugs.

Reaction of heteroaromatic o-aminothioaldehydes with alkynes: a novel entry to b-fused pyridines

Abstract o-Aminothioaldehydes derived from benzo[ b ]furan, benzo[ b ]thiophene, indole and furan rings smoothly react with mono- and disubstituted electron deficient alkynes to give b -fused dihydropyridines which can be converted to corresponding pyridines upon heating under vacuum.