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1.
Lucien Stella 《Angewandte Chemie (International ed. in English)》1983,22(5):337-350
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. 相似文献
2.
Lucien Birgé 《Probability Theory and Related Fields》1986,71(2):271-291
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.
This work was carried out during a visit of the author at the Mathematical Sciences Research Institute at Berkeley 相似文献
This work was carried out during a visit of the author at the Mathematical Sciences Research Institute at Berkeley 相似文献
3.
Heinz Günter Viehe Robert Mernyi Lucien Stella Zdenek Janousek 《Angewandte Chemie (International ed. in English)》1979,18(12):917-932
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. 相似文献
4.
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. 相似文献
5.
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. 相似文献
6.
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. 相似文献
7.
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. 相似文献
8.
2D difference gel electrophoresis reference map of a Fusarium graminearum nivalenol producing strain
Matias Pasquali Tommaso Serchi Jenny Renaut Lucien Hoffmann Torsten Bohn 《Electrophoresis》2013,34(4):505-509
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. 相似文献
9.
Lucien Eisenburger Prof. Dr. Oliver Oeckler Prof. Dr. Wolfgang Schnick 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4461-4465
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. 相似文献
10.