Novel Synthesis of (+/−)-cis-4-Amino-2-cyclopentene-1-methanol,a Key Intermediate in the Preparation of Carbocyclic 2′,3′-Didehydro-2′,3′-dideoxy Nucleosides

Abstract

Novel synthetic routes directed toward the preparation of (+/?)-cis -4-amino-2-cyclopentene-1-methanol are described. The routes investigated involve azide openings of chiral and non-chiral cyclopentyl epoxides.     

Interactions of polar hydrogen bond donor solvents with ions: a theoretical study

Structural Chemistry - Intermolecular interactions between molecules of protic solvents (water, methanol, formic acid, formamide, methylamine and ammonia) and monatomic ions (Li+, Na+, K+,...     

Synthesis and Tuberculostatic Activity of 1,3-Thiazacycloalkyl[3,2-b]-1,2,4-triazoles

The 4-hydroxyalkyl-1,2,4-triazole-3-thiones cyclization allowed us to work out the effective method of 1,3-thiazacycloalkyl[3,2-b]-1,2,4-triazoles synthesis. Some of the compounds that were obtained were tested for their tuberculostatic activity.     

Kinetic Studies of the Thermal cis-to-trans Isomerization of Dioxaphospholanes

By following a previously reported method,¹ the synthesis of r-2-alkoxy-cis-4-cis-5-dimethyl-1,3,2-λ³-dioxaphospholanes ligands (1 and 3) was carried out. The purpose of this work is the kinetic study of the inversion barrier at phosphorus for 1 and 3 and the comparison with the already informed dioxaphospholane 2. The kinetic measurements of the thermal isomerization cis-to-trans were performed by ³¹P NMR spectroscopy, observing a first order kinetics for both compounds. The energy of activation (E_a) for the epimerization of compounds cis-1 and cis-3 was calculated to be 16.0 ± 0.6 and 11.8 ± 0.8 kcal/mol, respectively. The values of the thermodynamic parameters of the transition state (Δ H^≠, Δ S^≠, Δ G^≠) suggest that the inversion at phosphorus not only depends on the spatial requirements of the alkoxy substituent but also on entropic effects. The thermodynamic parameters Δ H°, Δ S°, and Δ G° were also evaluated and they show that the cis isomers are preferred from enthalpic point of view, but entropic effects dominate the equilibrium trans ? cis leading to the entropically favored trans isomers. Furthermore, the results are supported by density functional theory calculations of 1–4 at the B3LYP/6-31G** level.