Phase transfer catalytic synthesis of silyl derivatives of heterocyclic thiols

Reactions of heteroaromatic thiols with trialkylsilylakyl iodides in the two-phase catalytic system (solid K₂CO₃/18-crown-6/toluene) at 111°C selectively lead to formation of the corresponding (trialkylsilylalkyl)thiohetarenes. 6-Mercaptopurine in the presence of two equivalents of alkylating agent yields S,N-dialkylated derivatives.Dedicated to the 100th anniversary of the birth of Academician A. N. Nesmeyanov.Latvian Institute of Organic Synthesis, Riga LV-1006, Latvia Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1197–1202, September, 1999.     

Catalytic enantioselective hydroboration of cyclopropenes

2,2-Disubstituted cyclopropyl boronates have been synthesized with high degrees of diastereo- and enantioselectivity via the rhodium-catalyzed asymmetric hydroboration of 3,3-disubstituted cyclopropenes. A strong directing effect of ester and alkoxymethyl substituents has been demonstrated. The directing effect was found to be necessary in achieving high degrees of enantiomeric induction. Selected cyclopropylboronic derivatives were successfully employed in the Suzuki cross-coupling reaction to produce the corresponding optically active aryl- and vinylcyclopropanes in good yields.     

Vapor phase oxidation of methylpyridines on zeolite catalysts

It has been established that zeolites containing Pd and Cu ions catalyze the vapor phase oxidation of methylpyridines. In oxidation of 2-methylpyridine on PdCuNa-mordenite at 375 °C the yield of 2-pyridinecarbaldehyde is 40 % of its theoretical values.

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, , Pd Cu, . 2- PdCuNa- 2- 375°C 40% .

     

Prototropic Rearrangement of 2-Propynyl(methyl)amino, 2-Propynyloxy,and 2-Propynylsulfanyl Derivatives of Hetarenes under Conditions of Phase-Transfer Catalysis: Mechanism and Limitations

2-Propynyl derivatives of N-methylaniline, phenol, benzenethiol, 2-pyridinethiol, 2-pyrimidinethiol, and 1,3-benzoxazole-2-thiol were synthesized. Under conditions of phase-transfer catalysis, phenyl 2-propynyl sulfide is converted into allenyl phenyl sulfide and phenyl 1-propynyl sulfide. The rearrangement mechanism was studied by the AM1 quantum-chemical method.     

Palladium-catalyzed highly chemo- and regioselective formal [2+2+2] sequential cycloaddition of alkynes: a renaissance of the well known trimerization reaction?

A new concept of highly chemo- and regioselective formation of the benzene ring by a palladium-catalyzed formal [2 + 2 + 2] sequential intermolecular trimerization of alkynes is proposed. Homodimerization of terminal alkynes and subsequent [4 + 2] benzannulation with diynes gives tetrasubstituted benzenes in moderate to good yields. The introduction of two different alkynes (terminal and internal) in the first step of the sequence allows for construction of pentasubstituted benzenes from three different acyclic acetylenic units. In all cases the tetra- and pentasubstituted benzenes are formed as a single reaction product without being accompanied by any of regio- or chemoisomers. A significant acceleration of the sequential trimerization reaction in the presence of Lewis acid/phosphine combined system was observed. Mechanistic studies reveal that the Lewis acid assisted isomerization of the E-enyne formed in the first step of the sequence to the more reactive Z-isomer is responsible for the observed acceleration effect. The proposed methodology provides a conceptually new and synthetically useful route to multifunctional aromatic compounds.     

On solving the potential equation

We study radial solutions to the generalized Swift-Hohenberg equation on the plane with an additional quadratic term. We find stationary localized radial solutions that decay at infinity and solutions that tend to constants as the radius increases unboundedly (“droplets”). We formulate existence theorems for droplets and sketch the proofs employing the properties of the limit system as r → ∞. This system is a Hamiltonian system corresponding to a spatially one-dimensional stationary Swift-Hohenberg equation. We analyze the properties of this system and also discuss concentric-wave-type solutions. All the results are obtained by combining the methods of the theory of dynamical systems, in particular, the theory of homo-and heteroclinic orbits, and numerical simulation.     

1,2-Halogen migration in haloallenyl ketones: regiodivergent synthesis of halofurans

Selective 1,2-iodine, bromine, and chlorine migration in haloallenyl ketones in the presence of Au catalyst has been demonstrated. It was found that, depending on the nature of the Au catalyst used, either selective bromine migration or hydrogen shift occurs, leading to the formation of 3- or 2-bromofurans, respectively. Halirenium intermediate was proposed for the unusual 1,2-halogen migration. This cascade transformation allows for mild and efficient synthesis of various types of 3-halofurans.     

Three-dimensional model of biomatrix as a method of studying blood vessels and nerve growth in tissue engineering structures

The method involves isolating and culturing ex vivo cultures of mouse dorsal root ganglia and abdominal aorta in a three-dimensional gel (Matrigel). Unlike other explant cultures, this technique allows to study the physiological and biochemical processes in the tissue explants of dorsal root ganglia and abdominal aorta in three-dimensional space but in contrast to a two-dimensional adhesive culture. Administration of the tested substances to the Matrigel allows analyzing their effects on the growth of blood vessels and neurites from the explants for 21 days. The developed method can be applied in modern cardiological and neurobiological research and explores how new therapeutic agents can accelerate the regeneration of blood vessels and nerves.     

Alkylation of Aryl and Hetaryl Ketoximes with Alkyl Iodides Prepared In Situ from Alkyl Chlorides Under Phase Transfer Catalysis Conditions

Two simple one-pot phase transfer catalytic methods for the preparation of ketoxime O-ethers from the corresponding ketoximes and alkyl iodides prepared in situ from alkyl chlorides were developed. The corresponding aryl and hetaryl ketoxime O-ethers were obtained in 15–83% yields.