Tandem nucleophilic addition-intramolecular aza-Michael reaction: facile synthesis of chiral fluorinated isoindolines

A highly stereoselective synthesis of fluorinated 1,3-disubstituted isoindolines is described. To this end, a tandem reaction consisting of a diastereoselective addition of fluorinated nucleophiles to Ellman's N-(tert-butanesulfinyl)imines followed by an intramolecular aza-Michael reaction has been developed. This strategy allows for the construction of isoindolines bearing several degrees of fluorination (mono-, di-, or trifluoromethyl as well as heavier fluorinated groups). In the majority of all cases, the products are formed as single isomers.     

Kinetics and mechanism of organocatalytic aza-Michael additions: direct observation of enamine intermediates

The imidazoles 1a-g add to the CC-double bond of the iminium ion 2 with rate constants as predicted by the equation log k = s(N)(N + E). Unfavourable proton shifts from the imidazolium unit to the enamine fragment in the adduct 3 account for the failure of imidazoles to take part in iminium-activated aza-Michael additions to enals.     

Solvent-free aza-Markovnikov and aza-Michael additions promoted by a catalytic amount of imidazolide basic ionic liquids

A family of imidazolide ionic liquids were synthesized and characterized. These ionic liquids combined the virtues of strong basicity and relatively good thermal stability. Catalytic properties of these imidazolide ionic liquids were investigated and satisfactory yield was achieved when 2.0 mol % of [Bmim]Im was used as catalyst for aza-Markovnikov addition under solvent-free condition at room temperature in one hour. Experimental results show that a hydrogen bond is not formed between [Bmim]Im/imidazole and vinyl ester, and its existence is not necessary for the [Bmim]Im catalyzed aza-Markovnikov addition either. A possible mechanism for [Bmim]Im-catalyzed aza-Markovnikov addition was proposed. The use of imidazolide ionic liquids in aza-Michael addition was investigated as well.     

Tandem cross metathesis and intramolecular aza-Michael reaction to synthesize bicyclic piperidines and indolizidine 167E

We have successfully transformed the terminal alkenes of dihydropyridones to the α,β-unsaturated esters by cross metathesis (CM). After detosylation the secondary amides can undergo the intramolecular aza-Michael reaction to give the bicyclic piperidine structures. The stereoselectivity of the aza-Michael reaction is determined by the size of the newly formed ring. With simple transformations we have also achieved the synthesis of indolizidine 167E.     

Regioselective aza-Michael additions of 2-arylidene-1,3-diphenylpropan-1,3-diones with isatins: Synthesis of N-diketone-functionalized isatins

The efficient aza-Michael additions of isatins to 2-arylidene-1,3-diphenylpropan-1,3-diones at room temperature in the presence of cesium carbonate are described. The salient features of this protocol are no transition-metal catalysts, mild conditions, high regioselectivity, high atom economy, satisfactory yield and simple work-up procedures.     

Protein aggregate structure under high pressure

We show that casein protein micelles--a complex protein/inorganic phosphate structure--can be subjected to high pressures (up to 350 MPa) while making in situ structural measurements using (ultra-)small angle neutron scattering, to give insight to the protein structure, aggregation and stability under pressure.     

Structural investigations under high pressure conditions

Because of its extremely high yield strength, hardness and relatively high transparency to high-energy x-ray radiation, the diamond anvil cell has become a favored device in high pressure research. This includes structural investigations where pressure induced phase transitions can be studied using x-ray diffraction techniques up to several Mbars when combined with a high-brilliance synchrotron source. In this paper several structural studies under high pressure are presented to show general trends. High pressure instrumentation has reached the stage at which hydrogen, according to theoretical calculations, can be metallized and thermodynamic conditions, (i.e. pressure and temperature) exceed those at the center of the earth.     

Dissociation of methane under high pressure

Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P2(1)2(1)2(1), Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C(2)H(6)) at 95 GPa, butane (C(4)H(10)) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune.     

Mukaiyama-Michael vinylogous additions to nitroalkenes under solvent-free conditions

The first Mukaiyama-Michael vinylogous reaction of a dioxinone-derived silyl ether to nitroalkenes is reported. The conjugate addition is performed in absence of any catalyst under solvent-free conditions, proceeding with satisfactory efficiency with variously substituted nitroalkenes.     

Cycloaddition of diazoacetic ester to 16-dehydropregnenolone acetate under high pressure

Conclusions The cycloaddition of ethyl diazoacetate to 16-dehydropregnenolone acetate under high pressure makes it possible to obtain, along with the known pyrazoline, the primary reaction product, namely the ¹-pyrazoline.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2374–2375, October, 1977.     

Emulsion polymerization of styrene under high pressure

Summary The emulsion polymerization of styrene was studied at 40 °C over a pressure range of 1 to 1000 bar. By measuring the ratio of the overall reaction rate under high pressure and at atmospheric pressure, the activation volume for the prouagation was obtained as –23.5 cm³/mol which was rather smaller than the literature values. The underestimation by the method of emulsion polymerization would be due to the character of polymerization processes and the emulsion polymerization method is not appropriate to determine the accurate value of the activation volume of propagation reactions.

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Zusammenfassung Es wird die Emulsionspolymerisation von Styrol bei 40 °C über den Druckbereich von 1 bis 1000 bar untersucht. Durch Messung des Verhältnisses der Reaktionsgeschwindigkeit unter hohem Druck und bei Atmosphärendruck wurde das Aktivierungsvolumen für die Ausbreitungsgeschwindigkeit zu –23,5 cm³/mol gefunden, ein Werr, der ziemlich kleiner als die Literaturwerte ist, Die Unterschätzung bei der Methode der Emulsionspolymerisation dürfte dem Charakter des Polymerisationsprozesses zuzuschreiben sein, und die Emulsionspolymerisation ist nicht geeignet, den exakten Wer für das Aktivierungsvolumen zu erhalten.

     

Free volumes in solids under high pressure

A review of experimental work on ortho-positronium (o-Ps) lifetime in solids under the pressures up to 1 GPa is presented. Among the effects observed at high pressure one can mention: the disappearance of the energy level for Ps at the reduction of free volume size; pressure induced phase transitions; variation of Ps formation intensity with time; increase of o-Ps lifetime after intercalation of high pressure gas to the paraffin samples.     

DTA measurements on polymers under high pressure

The construction of a high-pressure (up to 800 MPa), low-temperature (173–600 K) differential thermal analysis (DTA) apparatus is described. Some results on the phase transitions in polyethylene and poly(diethylsiloxane) under high pressure are presented.

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Zusammenfassung Mittels DSC wurde im Bereich 323 bis 1273 K die spezifische Wärme von Bi₄Ge₃O₁₂- und Bi₄Ti₃O₁₂-Einkristallen untersucht. Unter Zuhilfenahme des normalen Wärmekapazitätskurvenverlaufes für Bi₄Ge₃O₁₂ wurde derjenige Temperaturbereich bestimmt, in dem in Bi₄Ti₃O₁₂ die anomale Umwandlung von einer polarisierten in eine unpolarisierte Phase verläuft. Wärmeeffekt und Entropieänderung für diese Umwandlung wurden ermittelt.

     

Simulations of polymer crystallization under high pressure

High pressure crystallization of polypropylene was studied by means of PVT measurements and computer simulations. The isothermal crystallization behaviour were described by using a model which takes into account the effect of pressure on the temperature dependence of nucleation rate and linear growth rate. The agreement between the simulation and the experiments was seen in the tendency that the crystallization was accelerated by the high pressure. The non-isothermal crystallization behavior was also simulated by applying a generalized Avrami equation. The simulation curves well reproduced the experimental values below relative crystallinity 0.5 and below 100 MPa.     

Synthesis of 5-ketotetrazoles under high pressure

Conclusions The reaction of -ketonitriles with hydrazoic acid and organic azides at high pressure is an effective method for the synthesis of 5-acyltetrazoles.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1168–1170, May, 1988.     

Synthesis of titanium sulfides under high pressure

Titanium sulfides were synthesized in the temperature range 600–750°C and in the pressure range 10–200 MPa with an apparatus used for hydrothermal synthesis. Stoichiometric TiS₂ cannot be prepared under atmospheric pressure, but was synthesized under high pressure. Also the phase relationship between TiS₂ and TiS₃ has been established under high pressure up to 200 MPa, and the pressure-temperature phase diagram for TiS system is presented.