Experimental and Theoretical Studies on Acid Corrosion Inhibition of API 5L X70 Steel with Novel 1-N-α-d-Glucopyranosyl-1H-1,2,3-Triazole Xanthines.

A series of novel 1-N-α-d-glucopyranosyl-1H-1,2,3-triazole xanthines was synthesized from azido sugars (glucose, galactose, and lactose) and propargyl xanthines (theophylline and theobromine) using a typical copper (I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition. The corrosion inhibition activities of these new carbohydrate-xanthine compounds were evaluated by studying the corrosion of API 5 L X70 steel in a 1 M HCl medium. The results showed that, at 10 ppm, a 90% inhibition efficiency was reached by electrochemical impedance spectroscopy. The inhibitory efficiency of these molecules is explained by means of quantum chemical calculations of the protonated species with the solvent effect, which seems to better represent the actual situation of the experimental conditions. Some quantum chemical parameters were analyzed to characterize the inhibition performance of the tested molecules.

Stereocontrolled Nucleophilic Addition to Five-Membered Oxocarbenium Ions Directed by the Protecting Groups. Application to the Total Synthesis of (+)-Varitriol and of Two Diastereoisomers Thereof.

A stereodivergent C-glycosidation of carbohydrate-derived lactones can be mediated by the protecting groups and applied to the total synthesis of (+)-varitriol and of two diastereoisomers thereof, which represent an unprecedent use of the protecting groups in the synthesis of a naturally occurring compound. In particular, the stereoselective nucleophile attack for 2,3-trans-substituted five-membered ring oxocarbenium ions is strongly influenced by the presence of aromatic rings in the protecting groups. According to quantum chemical calculations, the stereoselectvity depends on the π-π interactions between the aromatic ring of the C-2 protecting group with the exocyclic triple bond and the oxocarbenium ion. These interactions account for the stabilization of the conformer in which the C-2 and C-3 substituents adopt pseudoaxial orientations. When protecting groups do not contain an aromatic ring, the sterochemical outcome is dictated by stereoelectronic factors established by the Woerpel's model. Based on these findings, a concise total synthesis of the natural product (+)-varitriol and of two diastereoisomers was acomplished.

ß-Oxygen effect in the Barton-McCombie deoxygenation reaction: further experimental and theoretical findings.

The chemistry of (S)-methyl xanthates derived from xylo- and ribo-furanose derivatives in the presence of the stannyl radical is investigated. Xanthate derived from ß-xylo-furanose affords exclusively a deoxygenated product; whereas, under the same reaction conditions, the α-ribo-furanose xanthate derivative produces quantitatively a hemithioacetal compound. We reasoned that in the case of the ß-xylo-furanose derivative, a favorable ß-oxygen effect in the Barton-McCombie deoxygenation reaction is operating where, according to theoretical calculations, unusual molecular orbital interactions (and not strain, as previously proposed) are present. These orbital interactions involve the SOMO (intermediary generated from the stannyl radical addition) with the σ* orbital of the bond undergoing cleavage and this with the two C-O antibonding orbitals anti oriented. Such molecular orbital interactions are not present in the α-ribo-furanose; therefore, the ß-scission is highly delayed, and due to the reversibly nature of the stannyl radical addition, the ribo-furanose xanthate is forced to take an alternative route: the homolytic substitution (S(H)2) of the sulfide sulfur by stannyl radical. This radical addition gives the alkoxythiocarbonyl radical, which is trapped by Bu3SnH before the elimination of carbonyl sulfide; subsequently, radical stannyl addition followed by radical reduction produces the hemithioacetal.

High 1,3-trans stereoselectivity in nucleophilic substitution at the anomeric position and ß-fragmentation of the primary alkoxyl radical in 3-amino-3-deoxy-ribofuranose derivatives: application to the synthesis of 2-epi-(-)-jaspine B.

The high inverse stereoselectivity in the nucleophilic substitution at the anomeric position of 3-amino-3-deoxy-ribofuranose derivatives is reported. This unprecedented stereoselectivity is explained in terms of preferential nucleophilic attack on the "inside face" of the respective five-membered ring oxocarbenium ion that orients pseudoequatorially to the benzylamine group placed at the C-3 position. In addition, an unusual ß-fragmentation of a primary alkoxyl radical generated from its corresponding N-phthalimide derivative was achieved, and thus taking advantages of both reactions, the total synthesis of 2-epi-(-)-jaspine B was completed.

Cu-Al mixed oxide-catalysed multi-component synthesis of gluco- and allofuranose-linked 1,2,3-triazole derivatives.

A series of carbohydrate-linked 1,2,3-triazole derivatives were synthesized in good yields from glucofuranose and allofuranose diacetonides using as key step a three-component 1,3-dipolar azide-alkyne cycloaddition catalysed by a Cu-Al mixed oxide. In this multi-component reaction, Cu-Al mixed oxide/sodium ascorbate system serves as a highly reactive, recyclable and efficient heterogeneous catalyst for the regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles. The reported protocol has significant advantages over classical CuI/N,N-diisopropylethylamine (DIPEA) or CuSO4/sodium ascorbate conditions in terms of efficiency and reduced synthetic complexity. In addition, the selective deprotection of synthesized di-O-isopropylidene derivatives was also carried out leading to the corresponding mono-O-isopropylidene products in moderate yields. Some of the synthesized triazole glycoconjugates were tested for their in vitro antimicrobial activity using the disc diffusion method against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa), as well as fungus (Aspergillus niger) and yeast (Candida utilis). The results revealed that these compounds exhibit moderate to good antimicrobial activity mainly against Gram-negative bacteria.