Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ³‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ³‐benziodoxolones are involved in these organocatalytic reactions.     

Operator–valued Fourier multiplier theorems on Besov spaces

We investigate analytical properties of a measure geometric Laplacian which is given as the second derivative w.r.t. two atomless finite Borel measures μ and ν with compact supports supp μ ? supp ν on the real line. This class of operators includes a generalization of the well‐known Sturm‐Liouville operator as well as of the measure geometric Laplacian given by . We obtain for this differential operator under both Dirichlet and Neumann boundary conditions similar properties as known in the classical Lebesgue case for the euclidean Laplacian like Gauß‐Green‐formula, inversion formula, compactness of the resolvent and its kernel representation w.r.t. the corresponding Green function. Finally we prove nuclearity of the resolvent and give two representations of its trace.     

Intramolecular meerwein reactions of the anthraquinone system. Synthesis,X-ray structural analysis and spectroscopic properties of anthra[9,1-bc:10,5-b'c']tetrahydrodipyran derivatives

Meerwein reactions of 1,5-anthraquinone bis(diazonium hydrogen sulfate) with sufficiently activated olefins, such as acrylonitrile, acrylic esters, methacrylonitrile and its esters, styrene and α-methylstyrene yielded derivatives of the new heterocyclic system anthra[9,1-bc:10,5-b'c']-2,3,7,8-tetrahydrodipyran. Isolation of derivatives was realized and yields enhanced by using dimethyl methylphosphonate as reaction medium. Compounds 5–18 were isolated as mixtures of diastereomers, some of which were separated by crystallization. Proof of structure and stereochemistry was obtained for some of the compounds by X-ray crystallographic analysis. The ¹H- and ¹³C-nmr data provided further support. Surprisingly large chemical shift differences between some of the proton signals of isomers were observed although the two asymmetric centers are far apart through bonds and through space. The mechanism of formation is explained on the basis of redox modulation of a charge transfer complex in which the aliphatic radical attacks the oxygen atom of the anthraquinone. It is proposed to classify this new type of reaction as an intramolecular Meerwein reaction.     

On the mechanical power transfer and unit-cell averaged energy-current density in general lattices

An elementary derivation is giveni) for the power transfer in a general system of coupled masses within the framework of classical mechanics andii) for the instantaneous energy-current density which is defined as an average over each unit celln. As a first application of these general expressions, it is shown for lattice waves in a general periodic harmonic lattice that the time average of the mentioned energy-current density is equal to the mean energy density times the group velocity.     

Carbonation of 3-pyridinols

Procedures are described for the high pressure carbonation of substituted 3-pyridinols, yielding the corresponding pyridine carboxylic acids. Treatment of o-aminohydroxypyridinecarboxylic acid with cyanogen and with phosgene, respectively, gave access to oxazolo[4,5-b]pyridine derivatives. The synthesis of 3-amino-6-methyl-2-pyridinecarboxylic acid was accomplished by heating 3-hydroxy-6-methyl-2-pyridinecarboxylic acid in liquid ammonia.     

Hydrazones and new Oximes of 4-Aminobicyclo[2.2.2]octanones and their Antiprotozoal Activities

Summary. 4-Aminobicyclo[2.2.2]octan-2-ones and -ols showed activity against the causative organisms of East African sleeping sickness and Malaria tropica. Several imino derivatives of the ketones were more active. Now hydrazono analogues and 3-hydroximino derivatives of the ketones and alcohols were synthesized. The structures of the obtained isomers were elucidated by NMR spectroscopy. A single phenylhydrazone exhibited quite good antitrypanosomal activity in the range of already known imino analogues.     

Hydrazones and new Oximes of 4-Aminobicyclo[2.2.2]octanones and their Antiprotozoal Activities

4-Aminobicyclo[2.2.2]octan-2-ones and -ols showed activity against the causative organisms of East African sleeping sickness and Malaria tropica. Several imino derivatives of the ketones were more active. Now hydrazono analogues and 3-hydroximino derivatives of the ketones and alcohols were synthesized. The structures of the obtained isomers were elucidated by NMR spectroscopy. A single phenylhydrazone exhibited quite good antitrypanosomal activity in the range of already known imino analogues.     

Characterization of the monovalent ion position and hydrogen-bond network in guanine quartets by DFT calculations of NMR parameters

Conformational stability of G-quartets found in telomeric DNA quadruplex structures requires the coordination of monovalent ions. Here, an extensive Hartree-Fock and density functional theory analysis of the energetically favored position of Li+, Na+, and K+ ions is presented. The calculations show that at quartet-quartet distances observed in DNA quadruplex structures (3.3 A), the Li+ and Na+ ions favor positions of 0.55 and 0.95 A outside the plane of the G-quartet, respectively. The larger K+ ion prefers a central position between successive G-quartets. The energy barrier separating the minima in the quartet-ion-quartet model are much smaller for the Li+ and Na+ ions compared with the K+ ion; this suggests that K+ ions will not move as freely through the central channel of the DNA quadruplex. Spin-spin coupling constants and isotropic chemical shifts in G-quartets extracted from crystal structures of K+- and Na+-coordinated DNA quadruplexes were calculated with B3LYP/6-311G(d). The results show that the sizes of the trans-hydrogen-bond couplings are influenced primarily by the hydrogen bond geometry and only slightly by the presence of the ion. The calculations show that the R(N2N7) distance of the N2-H2...N7 hydrogen bond is characterized by strong correlations to both the chemical shifts of the donor group atoms and the (h2)J(N2N7) couplings. In contrast, weaker correlations between the (h3)J(N1C6') couplings and single geometric factors related to the N1-H1...O6=C6 hydrogen bond are observed. As such, deriving geometric information on the hydrogen bond through the use of trans-hydrogen-bond couplings and chemical shifts is more complex for the N1-H1...O6=C6 hydrogen bond than for the N2-H2...N7 moiety. The computed trans-hydrogen-bond couplings are shown to correlate with the experimentally determined couplings. However, the experimental values do not show such strong geometric dependencies.     

3,6,9,10-tetrahalogenphenanthrene. A new cycliarylation reaction of DDT-derivatives

A simple synthesis of tetrachlorophenanthrene starting from DDT has been realized. 1,1,1,2-tetrachloro-2,2-bis-(4-chlorophenyl)-ethane (I) and its rearranged product 1,1,2,2-tetrachloro-1,2-bis-(4-chlorophenyl)-ethane (V) and other analogs substituted by halogen in the para-position undergo a cycliarylation yielding 3,6,9,10-tetrahalogenophenanthrenes. Partial dechlorination of this tetrachlorophenanthrene yields 3,6-dichlorophenanthrene. Oxidation gives 3,6-dichloro-9,10-phenanthrenequinone, and chlorosulfonation leads to 3,6,9,10-tetrachloro-2,7-bis-(chlorosulfonyl)-phenanthrene. The mechanism of this cyclization reaction in presence of LEWIS acids is discussed and compared with the cyclization of DDT derivatives to yield fluorenones.