Jean-Francois Lavallee

A comprehensive thermodynamic investigation of water-ethylene glycol mixtures at 5, 25, and 45°C

A detailed thermodynamic study of water (W)-ethylene glycol (EG) mixtures has been carried out as function of temperature (5, 25 and 45°C) and over the entire composition range. The data comprise heats of mixing, densities, heat capacities and compression coefficients. Using excess free energy data from earlier work, molar excess functions were calculated for free energies GE, enthalpies HE and entropies TSE, volumes VE, isobaric and isochoric heat capacities CPE, CVE, adiabatic and isothermal compression KE, KTE and thermal expansion EE, as well as the temperature derivatives of K, C and E functions. The corresponding partial molar quantities were also calculated except for G, H and S and are reported for both EG and W. Also calculated were cohesive energy density, internal pressure and Kirkwood-Buff integrals. The data reported here for EG-W mixtures are compared with similar data for other mixtures as available in order to gain insight into: 1) the relative discriminating ability of various thermodynamic coefficients towards weak cooperative intermolecular interactions in liquids; 2) the quantitative similarities and differences between liquid water and ethylene glycol; 3) the intermolecular phenomena which dominate the properties of EG-W mixtures of varying composition; 4) the usefulness of a qualtitative description of liquid water proposed by Lumry et al. which involves hydrogen-bonding interactions, hydrogen-bonding connectivity and small cooperative fluctuation units.

One-step construction of a 13α-methyl 14α-hydroxy steroid via a new anionic polycyclization method

Abstract The base-catalyzed reaction of 2-carbomethoxy-2-cyclohexenone (6) with the substituted Nazarov reagent 5 yields directly the tetracyclic β-ketoester 8 which upon decarboalkoxylation gives 13α-methyl-14α-hydroxy steroid 9.

Intramolecular Michael addition of cyclic β-ketoester on conjugated acetylenic ketone.

Abstract A study on the base-catalyzed intramolecular Michael addition of β-ketoester-ynone 1 (n′ = 1–2, n = 0–3) is reported.

Synthesis of cis-decalin via Diels-Alder and double Michael cycloaddition with substituted Nazarov reagent

Abstract The base-catalyzed cycloaddition of the methyl substituted Nazarov reagent 2 with 2-carbomethoxy-2-cyclohexenone ( 1 ) yielding cis-decalin products is reported.

Isoquinoline-6-carboxamides as potent and selective anti-human cytomegalovirus (HCMV) inhibitors.

Structure-activity relationship studies on our newly identified anti-HCMV compounds, the 1,6-naphthyridines led to the identification of isoquinoline-6-carboxamides as potent and selective anti-HCMV agents.

Intramolecular Michael addition of cyclic β-ketoester on conjugated olefinic ketone, a stereoelectronically controlled process

Abstract A study on the base-catalyzed intramolecular Michael addition of cyclic β-ketoester enones 9 and 10 (n = 0-3, R 1 = R 2 = H and/or CH 3 ) is reported.

Synthesis of tricyclic compounds via sequential intramolecular Michael addition and alkylation of β-ketoester ynones

Abstract Base-catalyzed sequential intramolecular Michael addition and alkylation of cyclic β-ketoester ynones 1 (n = 1,2) produce the corresponding tricycles 3 via intermediate enone-anions 2.

Substituted 1,6-naphthyridines as human cytomegalovirus inhibitors: conformational requirements.

Substituted 1,6-naphthyridine derivatives, a new class of human cytomegalovirus inhibitors, were prepared to demonstrate the role of intramolecular hydrogen bonds to maintain the compounds in their active conformation.

Synthesis and in vitro cytotoxicity of cryptophycins and related analogs

Abstract Several members of the Cryptophycin family were synthesised using a straightforward convergent approach. The proposed synthetic route was used to prepare novel analogs of Cryptophycins A and B in which the benzylic epoxide moiety was replaced by alternate electrophilic functions. The effect of these modifications on cytotoxic activity was determined on several tumor cell lines.

Synthesis of a 5-deoxypyranoanthracycline : An entry into novel analogs of idarubicin

Abstract This paper describes a convergent and regioselective synthesis of 5-deoxypyranoanthracycline 2 using pyranoquinone 12 which is a versatile intermediate for the synthesis of this new class of heteroanthracyclines.