Screening of highly modular sugar-based ligand libraries in the enantioselective C-C coupling reactions

Projecte de recerca elaborat a partir d’una estada a la University of Nottingham, Gran Bretanya, entre març i abril del 2007. Aquest treball s’ha centrat en l’aplicació de compostos derivats de la D-(+)-glucosa, de la D-(+)-fructosa i la D-galactosa com a lligands de catalitzadors homogenis quirals en dos reaccions asimètriques: addició 1,2 a aldehids catalitzada per níquel i addició 1,4 conjugada catalitzada per coure.(veure figura adjunta al final del document). En primer lloc, s’ha estudiat l’aplicació dels compostos L1-L6 a les reaccions d’addició 1,2 a aldehids catalitzades per níquel. S’ha observat que la selectivitat del procés depèn principalment del grup funcional unit a l’esquelet del lligand, de les propietats estèriques del substituent en la funció oxazolina i de l’estructura del substrat. S’ha obtingut fins a un 59% d’excés enantiomèric utilitzant el precursor de catalitzador que conté el lligand L3a. En segon lloc, aquest treball descriu l’aplicació de les tres famílies de compostos (L1-L11) com a lligands en la reacció d’addició 1,4 catalitzada per coure de compostos organometàl•lics a diferents enones amb diferents propietats estèriques. L’ús de les llibreries de compostos fosfit-oxazolina (L1-L5) i fosfit-fosforamidit (L6) han proporcionat bones enantioselectivitats (fins a 80%) en l’addició de reactius de trialquilalumini a diferents enones. En canvi, la llibreria de compostos monofosfit (L7-L11) ha mostrat bones activitats però enantioselectivitats fins a 57%.

Divergent Reactions to Globalization: Labor Unions and the Nafta and the EU Enlargement Process

The 1990s witnessed the launching of two ambitious trade regionalization plans, the Nafta and EU enlargement to Central and Eastern Europe. In contrast to previous projects for the creation or expansion of regional trade blocs, these two projects concerned states at dramatically different levels of economic development: The Nafta involved the very wealthy economies of Canada and the USA and the significantly poorer economy of Mexico, whereas EU enlargement involved the very wealthy economy of the 15 member-state European Union and the significantly poorer economies of former Communist states in Central and Eastern Europe. Ultimately, the Nafta and EU enlargement are responses to the challenges of globalization. Paradoxically, however, they have been met with radically different societal reactions in the wealthy partners that participated in the launching of these processes. This paper focuses on the reaction by labor unions on both sides of the Atlantic. I conclude that while labor relations and welfare institutions constrained the trade policy choices made by labor unions in the United States and Europe, they do not tell the whole story. It would seem that United States labor unions were more sensitive to the potential risks for workers associated to the liberalization of trade than were their European counterparts.

Teachers' reactions on students' responses: essential for an adequate task monitoring

This research project analyzes the reactions the teacher has on students' responses. Different techniques as discourse markers, types of questions and repair sequences are taken into account, but the author puts a special emphasis on non-verbal communication. To be aware of all these ways of reacting in a class interaction is essential for an adequate task monitoring

Does the sun shine by p p or CNO fusion reactions?

We show that solar neutrino experiments set an upper limit of 7.8% (7.3% including the recent KamLAND measurements) to the fraction of energy that the Sun produces via the CNO fusion cycle, which is an order of magnitude improvement upon the previous limit. New experiments are required to detect CNO neutrinos corresponding to the 1.5% of the solar luminosity that the standard solar model predicts is generated by the CNO cycle.

Evidence of chemical reactions in the hydroxyapatite laser ablation plume with a water atmosphere

The expansion dynamics of the ablation plume generated by KrF laser irradiation of hydroxyapatite targets in a 0.1 mbar water atmosphere has been studied by fast intensified charge coupled device imaging with the aid of optical bandpass filters. The aim of the filters is to isolate the emission of a single species, which allows separate analysis of its expansion. Images obtained without a filter revealed two emissive components in the plume, which expand at different velocities for delay times of up to 1.1 ¿s. The dynamics of the first component is similar to that of a spherical shock wave, whereas the second component, smaller than the first, expands at constant velocity. Images obtained through a 520 nm filter show that the luminous intensity distribution and evolution of emissive atomic calcium is almost identical to those of the first component of the total emission and that there is no contribution from this species to the emission from the second component of the plume. The analysis through a 780 nm filter reveals that atomic oxygen partially diffuses into the water atmosphere and that there is a contribution from this species to the emission from the second component. The last species studied here, calcium oxide, was analyzed by means of a 600 nm filter. The images revealed an intensity pattern more complex than those from the atomic species. Calcium oxide also contributes to the emission from the second component. Finally, all the experiments were repeated in a Ne atmosphere. Comparison of the images revealed chemical reactions between the first component of the plume and the water atmosphere.

Stereoselective Acetate Aldol Reactions From Metal Enolates

This review deals with metal enolate-mediated stereoselective acetate aldol reactions. It summarizes recent advances on aldol additions of unsubstituted metal enolates from chiral auxiliaries, stoichiometric and catalytic Lewis acids, or acting in substrate- controlled reactions, which provide stereocontrolled aldol transformations that allow the efficient synthesis of structurally complex natural products.

Preparation of alpha-labeled aldehydes by base-catalyzed exchange reactions

A simple, efficient protocol for the preparation of α-labeled aldehydes based on H/D exchange catalyzed by 4-(N,N-dimethylamino)pyridine or Et3N is described. High chemical yields and ratios of isotope incorporation were obtained even when small amounts (1 mmol) of aldehyde were used.

Preparation of alpha-labeled aldehydes by base-catalyzed exchange reactions

A simple, efficient protocol for the preparation of α-labeled aldehydes based on H/D exchange catalyzed by 4-(N,N-dimethylamino)pyridine or Et3N is described. High chemical yields and ratios of isotope incorporation were obtained even when small amounts (1 mmol) of aldehyde were used.

Complexes of Pd(II) and Pt(II) with 9-aminoacridine: reactions with DNA and study of their antiproliferative activity

Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO)2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.

Complexes of Pd(II) and Pt(II) with 9-aminoacridine: reactions with DNA and study of their antiproliferative activity

Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO)2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.

Complexes of Pd(II) and Pt(II) with 9-aminoacridine: reactions with DNA and study of their antiproliferative activity

Four new metal complexes {M = Pd(II) or Pt(II)} containing the ligand 9-aminoacridine (9AA) were prepared. The compounds were characterized by FT-IR and 1H, 13C, and 195Pt NMR spectroscopies. Crystal structure of the palladium complex of formulae [Pd(9AA)(μ-Cl)]2 · 2DMF was determined by X-ray diffraction. Two 9-acridine molecules in the imine form bind symmetrically to the metal ions in a bidentate fashion through the imine nitrogen atom and the C(1) atom of the aminoacridine closing a new five-membered ring. By reaction with phosphine or pyridine, the Cl bridges broke and compounds with general formulae [Pd(9AA)Cl(L)] (where L = PPh3 or py) were formed. A mononuclear complex of platinum of formulae [Pt(9AA)Cl(DMSO)] was also obtained by direct reaction of 9-aminoacridine and the complex [PtCl2(DMSO)2]. The capacity of the compounds to modify the secondary and tertiary structures of DNA was evaluated by means of circular dichroism and electrophoretic mobility. Both palladium and platinum compounds proved active in the modification of both the secondary and tertiary DNA structures. AFM images showed noticeable modifications of the morphology of the plasmid pBR322 DNA by the compounds probably due to the intercalation of the complexes between base pairs of the DNA molecule. Finally, the palladium complex was tested for antiproliferative activity against three different human tumor cell lines. The results suggest that the palladium complex of formula [Pd(9AA)(μ-Cl)]2 has significant antiproliferative activity, although it is less active than cisplatin.

Dynamic and quasistatic trajectories in quasifission reactions and particle emission

We show that the quasifission paths predicted by the one-body dissipation dynamics, in the slowest phase of a binary reaction, follow a quasistatic path, which represents a sequence of states of thermal equilibrium at a fixed value of the deformation coordinate. This establishes the use of the statistical particle-evaporation model in the case of dynamical time-evolving systems. Pre- and post-scission multiplicities of neutrons and total multiplicities of protons and α particles in fission reactions of 63Cu+92Mo, 60Ni+100Mo, 63Cu+100Mo at 10 MeV/u and 20Ne+144,148,154Sm at 20 MeV/u are reproduced reasonably well with statistical model calculations performed along dynamic trajectories whose slow stage (from the most compact configuration up to the point where the neck starts to develop) lasts some 35×10−21 s.

Conjugation reactions involving maleimides and phosphorothioate oligonucleotides

Phosphorothioate diester oligonucleotides proved to be fully compatible with maleimides in the context of two different conjugation reactions: (a) reaction of 5′diene-[phosphorothioate oligonucleotides] with maleimido-containing compounds to afford the Diels-Alder cycloadduct; (b) conjugation of 5′maleimido-[phosphorothioate oligonucleotides] with thiol-containing compounds. No evidence of reaction between phosphorothioate diesters and maleimides was found in any of these processes. Importantly, in the preparation of 5′maleimido-[phosphorothioate oligonucleotides] from [protected maleimido]-[phosphorothioate oligonucleotides], which requires the maleimide to be deprotected by retro-Diels-Alder reaction (heating for 3-4 h in toluene at 90 °C), no addition of phosphorothioate diester to the maleimide was found either. Finally, maleimide-[phosphorothioate monoester] conjugation was also explored for comparison purposes.

Fmoc-2-Mercaptobenzothiazole (MBT), for the Introduction of the Fmoc Moiety Free of Side-Reactions

A double side-reaction, consisting in the formation of Fmoc--Ala-OH and Fmoc--Ala-AA-OH, during the preparation of Fmoc protected amino acids (Fmoc-AA-OH) with Fmoc-OSu is discussed. Furthermore, the new Fmoc-2-MBT reagent is proposed for avoiding these side-reactions as well as the formation of the Fmoc-dipeptides (Fmoc-AA-AA-OH) and even tripeptides, which is another important side-reaction when chloroformates such as Fmoc-Cl is used for the protection of the -amino function of the amino acids.