Homolytic Cyclizations of N-Chloroalkenylamines

Many N-chloroalkylamines with double bond(s) dissociate homolytically to give chlorine atoms and aminyl radicals which undergo intramolecular cyclization reactions. Here, the nature of the aminyl radicals (neutral, protonated, or complexed to metal salts) appears to be important. The reactivity varies strongly from one species to another, and their selectivities can be different towards addition, substitution, abstraction, or dimerization reactions. A good synthetic tool appears to be the “complexed radical”, which is generated under mild conditions. A variety of β-functionalized, substituted, fused, or bridged azaheterocycles with alkaloid part structures thus become easily accessible in high yields, in a regio- and, possibly, stereoselective manner. Many examples are discussed illustrating the synthetic possibilities, limitations, and mechanistic features of this cyclization process.     

On estimating a density using Hellinger distance and some other strange facts

Résumé On s'intéresse ici aux possibles vitesses d'estimation d'une densité à support compact dans ^m sous des hypothèses de régularité, lorsque la perte est mesurée par le carré de la distance de Hellinger (on regardera aussi le cas connu des normes pour 1q2) et le risque est le risque minimax sur la famille. On donne une méthode générale permettant de traiter les problèmes dans le cadre de la théorie de l'approximation sous des conditions concernant l'entropie métrique et l' -capacité des familles à estimer. Les rapports entre régularité et entropie métrique étant bien connus, nous pourrons aussi traiter les cas classiques et d'autres qui le sont moins. Sous des conditions de bornes inférieures les vitesses sont celles observées pour la norme mais elles diffèrent dans le cas général. On montre aussi que les restrictions sur la compacité du support ou la régularité sont indispensables et que leur absence mène à l'impossibilité d'obtenir une estimation raisonnable en ce sens que n'importe quelle suite d'estimateurs sera arbitrairement mauvaise en un point au moins. Un résultat analogue est vrai sous des conditions de régularité.

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This work was carried out during a visit of the author at the Mathematical Sciences Research Institute at Berkeley     

Capto-dative Substituent Effects in Syntheses with Radicals and Radicophiles [New synthetic methods (32)]

The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals.     

Cyphostemmins A-B, two new antifungal oligostilbenes from Cyphostemma crotalarioides (Vitaceae)

Two new antifungal resveratrol dimers, cyphostemmins A-B (1–2), have isolated from the roots of Cyphostemma crotalarioides planch (Vitaceae) together with resveratrol 3 and previously known reseveratrol dimers (4–7). Structures of these new compounds have been established on the basis of their MS and ¹H and ¹³C NMR spectroscopic data.     

QUENCHING OF SINGLET OXYGEN BY SENSITIZER IN DYE-SENSITIZED PHOTOOXYGENATION*

Abstract— A general method for the determination of the extent of the singlet oxygen (¹O₂) quenching by sensitizer in the dye-sensitized photooxygenation of olefins is used in the case of rose bengal (RB) in methanol and oil-soluble chlorophyll (M) in benzene with 2-methyl-2-pentene and tetramethylethylene as acceptors. Unlike RB, M which contains only a low percentage of pure chlorophyll (Chi), quenches ¹O₂. It is shown that this very cheap mixture can be used for kinetic studies and that the chemical quenching of ¹O₂ by M is very weak with respect to the physical quenching. The upper limit for the rate constants of physical and chemical quenching of ¹O₂ by Chi is estimated.     

Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical.     

A Novel and Cheap Synthesis of Artemisia Ketone1 (3,3,6-Trimethylhepta-L,5-Dien-4-One)

The Sequential dialkylation of dimethylaminoacetonitrile with first methallylchloride and then prenylbromide is performed at room temperature using K₂CO₃ in DMF. Subsequent hudrolysis and isomerisation offord artemisia ketone in 77% overall yield.     

Stereoselective Cycloaddition of Monosubstituted Ketene to a Methyl Glyoxylate- and Threonine-Derived Imine: Synthesis of Optically Pure β-Lactamic α-Amino Ester with High Functionality

The reaction of chloroacetyl chloride and triethylamine with a chiral imine derived from the combination of methyl glyoxylate and protected L-threonine gave two optically active α-amino acid derivatives with a cis-substituted β-lactam skeleton in a 72:28 ratio. The major product is obtained in 59% yield by simple crystallisation.     

2D difference gel electrophoresis reference map of a Fusarium graminearum nivalenol producing strain

Fusarium graminearum is widely studied as a model for toxin production among plant pathogenic fungi. A 2D DIGE reference map for the nivalenol‐producing strain 453 was established. Based on a whole protein extract, all reproducible spots were systematically picked and analyzed by MALDI‐TOF/TOF, leading to the identification of 1102 protein species. The obtained map contributes to the annotation of the genome by identifying previously nondescribed hypothetical proteins and will serve as a reference for future studies aiming at deciphering F. graminearum biology and chemotype diversity.     

High-Pressure High-Temperature Synthesis of Mixed Nitridosilicatephosphates and Luminescence of AESiP3N7:Eu2+ (AE=Sr,Ba)

Tetrahedra-based nitrides with network structures have emerged as versatile materials with a broad spectrum of properties and applications. Both nitridosilicates and nitridophosphates are well-known examples of such nitrides that upon doping with Eu²⁺ exhibit intriguing luminescence properties, which makes them attractive for applications. Nitridosilicates and nitridophosphates show manifold structural variability; however, no mixed nitridosilicatephosphates except SiPN₃ and SiP2N4NH have been described so far. The compounds AESiP₃N₇ (AE=Sr, Ba) were synthesized by a high-pressure high-temperature approach using the multianvil technique (8 GPa, 1400–1700 °C) starting from the respective alkaline earth azides and the binary nitrides P₃N₅ and Si₃N₄. The latter were activated by NH₄F, probably acting as a mineralizing agent. SrSiP₃N₇ and BaSiP₃N₇ were obtained as single crystals. They crystallized in the barylite-1O (M=Sr) and barylite-2O structure types (M=Ba), respectively, with P and Si being occupationally disordered. Cation disorder was further supported by solid-state NMR spectroscopy and energy-dispersive X-ray spectroscopy (EDX) mapping of BaSiP₃N₇ with atomic resolution. Upon doping with Eu²⁺, both compounds showed blue emission under UV excitation.