Synthetic applications of aryl radical building blocks for cyclisation onto azoles

2-(2-Bromophenyl)ethyl groups have been used as building blocks in radical cyclisation reactions onto azoles to synthesise tri- and tetra-cyclic heterocycles. 2-(2-Bromophenyl)ethyl methanesulfonate was used to alkylate azoles (imidazoles, pyrroles, indoles and pyrazoles) for the synthesis of the radical precursors. Cyclisations of the intermediate aryl radicals yield new 6-membered rings attached to the azoles. The aryl radicals undergo intramolecular homolytic aromatic substitution onto the azole rings. Tributylgermanium hydride has been used with success to replace the toxic and troublesome tributyltin hydride. Initial studies show that the protocol can be used on solid phase resins. The molecular and crystal structures of methyl 5,6-dihydroimidazo[5,1-a]iso-quinoline-1-carboxylate and methyl 5,6-dihydroimidazo[2,1-a]isoquinoline-3-carboxylate were determined by X-ray crystallography.     

Grassmann manifold of aJH-algebra

We study the set of rankp idempotents in a topologically simple Hilbert Jordan algebra (JH-algebra for short). To produce the differential geometric structure on, we establish Jordan algebraic results concerning the structure of some two-generator subalgebras. We identify geodesics, the Riemannian distance and the sectional curvature of by using the Jordan algebraic structure.     

Some remarks on the modulus of continuity of a conformal mapping of the disk onto a Jordan domain

Letd(;z, t) be the smallest diameter of the arcs of a Jordan curve with endsz andt. Consider the rapidity of decreasing ofd(;)=sup{d(;z, t):z, t , ¦z–t¦} (as 0,0) as a measure of nicety of . Letg(x) (x0) be a continuous and nondecreasing function such thatg(x)x,g(0)=0. Put¯g(x)=g(x)+x, h(x)=(¯g(x))². LetH(x) be an arbitrary primitive of 1/h ^–1(x). Note that the functionH ^–1 x is positive and increasing on (–, +),H ^–1 0 asx– andH ^–1+ asx +. The following statement is proved in the paper.Translated fromMatematicheskie Zametki, Vol. 60, No. 2, pp. 176–184, August, 1996.This research was supported by the Russian Foundation for Basic Research under grant No. 93-01-00236 and by the International Science Foundation under grant No. NCF000.     

Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either 1-phenylethylbromide or 1,4-dibromoxylene as initiators for ATRP. Diverse bromo(ester) (macro)initiators were also devised and involved in the formulation of fluorinated pentablock as well as amphiphilic triblock copolymers with a central polyether segment. Amphiphilic star-shaped fluoropolymers, hydrophobic fluorinated nanoparticles, or segmented fluorinated star-shaped block copolymers are further designed by use of different multifunctional initiators. The composition of the novel materials with PFS is determined by combination of SEC and ¹H NMR. Glass transition temperatures and thermal stabilities of the hydrophobic star-shaped PFSs on a six arm dipentaerythritol core are investigated in a wide range of molecular masses and further discussed.     

Fluoride-induced coupling of perfluoroketene dithioacetals with silyl alkynes: A way towards new polyfunctionalized trifluoromethyl building blocks

Under fluoride activation, the vinyl fluorine of perfluoroketene dithioacetal may be substituted by silylated nucleophiles. Using silyl alkynes, a formal transition metal free sila-Sonogashira cross-coupling reaction occurred. The resulting enynes were hydrolyzed giving new polyfunctional trifluoromethyl building blocks.     

Microwave-assisted cleavage of Weinreb amide for carboxylate protection in the synthesis of a (R)-3-hydroxyalkanoic acid

A versatile route for the modular synthesis of (R)-3-hydroxyalkanoic acids, constituents of the naturally biodegradable poly(3-hydroxyalkanoate) polymers, and its application to the synthesis of (R)-3-hydroxydecanoic acid is described. Key steps include a microwave-assisted catalytic transfer hydrogenation and a facile microwave-assisted hydrolysis of an N-methoxy-N-methyl (Weinreb) amide, which enhances the practicality of this protecting group for carboxylic acids.     

The First Catalytic Synthesis of an Acrylate from CO2 and an Alkene—A Rational Approach

For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C₁ building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO₂, ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.     

Thiadiazolo-Azaacenes

This work reports the synthesis and characterization of bis- and tetrakis(thiadiazolo)-appended di- and tetraazaacenes, displaying up to seven catenated benzene/pyrazine rings. The targets are obtained by condensation of benzo-bis(thiadiazole)-4,5-dione with aromatic di- and tetraamines. The condensation products—up to a heptacene-like species—are stable but can be insoluble. Soluble derivatives are readily processible, but do not show enhanced electron affinities, as the two or four attached benzothiadiazole units are effectively resonance-separated from the acene body, maximizing the number of Clar-sextets.     

Jordan operator algebras revisited

Jordan operator algebras are norm‐closed spaces of operators on a Hilbert space with for all . In two recent papers by the authors and Neal, a theory for these spaces was developed. It was shown there that much of the theory of associative operator algebras, in particular, surprisingly much of the associative theory from several recent papers of the first author and coauthors, generalizes to Jordan operator algebras. In the present paper we complete this task, giving several results which generalize the associative case in these papers, relating to unitizations, real positivity, hereditary subalgebras, and a couple of other topics. We also solve one of the three open problems stated at the end of our earlier joint paper on Jordan operator algebras.