A short route to enantiomerically pure benzophenanthridinone skeleton: synthesis of lactone analogues of narciclasine and lycoricidine

Condensation of functionalized o-toluamide anions on a carbohydrate-derived lactone, followed by intramolecular aldol cyclization, provides enantiomerically pure 2-arylcyclohexenones. Different approaches for the stereoselective transformation of the carbonyl group of these key intermediates into an amino group were unsuccessful. However 1,4-addition of thiolate and concomitant ring closure to isocoumarine provided a useful method for the transformation of the tertiary amide function. Opening of the isocoumarin with ammonia provided the corresponding amide and recovery of the enone system. Subsequent reductive amination of this cyclohexenone was found to depend on the nature of the protecting groups and led to the protected form of 4-epi- and -iso-narciclasine. Oxo analogues of narciclasine and epi-narciclasine and lycoricidine were also obtained after reduction of the enone and subsequent lactonization. They showed no biological activity as antitumor agents.     

Réactions de Friedel et Crafts de dérivés aromatiques sur les composés dioxo-1,4,2,3-non saturés. IV. Réactions des hydroxy-5-ouchloro-5-diméthyl-3,5- ou diméthyl-4,5-dihydro-2,5-furannones-2

Friedel-Crafts reactions of aromatic derivatives with 1,4-dicarbonyls 2,3-éthylenic compounds. Part IV. Reactions of 5-hydroxy or 5-chloro 3,5-dimethyl or 4,5-dimethyl 2 (5 H) furanones We studied the Friedel-Crafts reactions of 2-(5H)-furanones. In the presence of sulfuric acid and of an aromatic derivative, 5-hydroxy- or 5-chloro-5-methyl-2-(5H)-furanones with one methyl group either in the 3 position, or in the 4 position generally give the corresponding 5-aryl-2-(5H)-furanones, while with aluminium chloride, it is possible to obtain, when a reaction takes place, isomeric 1H-indenecarboxylic acids. However, in a particular case, an addition to the substrate's double bond is observed. The 3-aryl-5-hydroxy-tetrahydrofuran-2-one obtained is methylated in two ways and gives either a cyclic product, or a linear one. In two cases tautomerism between 1H-1-indenecarboxylic acid and 1H-3-indenecarboxylic has been shown by ¹H-NMR.     

Ergodic theory of the mixmaster universe in higher space-time dimensions. II

The topological dynamics of the mixmaster models in space-time dimension d+1 are investigated. We use a new parametrization to reduce the mixmaster map to a translation combined with an appropriate isometry or a dilating inversion. For d9, we show that the mixmaster map is ergodic and topologically mixing. For d10, the mixmaster map reduces to the identity after a finite number of iterations, except for a set of initial data with zero Lebesgue measure.Chargé de recherches au Fonds National de la Recherche Scientifique.     

Catalytic oxidation of α-pinene by transition metal using t-butyl hydroperoxide and hydrogen peroxide

The allylic oxidation of α-pinene 1 was investigated using various catalytic systems. By a proper choice of the latter, the reaction can be directed toward the selective synthesis of verbenol 2 or verbenone 3. High yield into verbenone was achieved under mild conditions with copper salts as catalysts and t-butyl hydroperoxide (TBHP) as oxidant. On the other hand, when Pd(acac)₂ was used with hydrogen peroxide, verbenol was obtained as the main product.     

Unconventional temperature dependence of the cuprate excitation spectrum

Key properties of the cuprates, such as the pseudogap observed above the criticaltemperature T_c, remain highlydebated. Given their importance, we recently proposed a novel mechanism based on theBose-like condensation of mutually interacting Cooper pairs [W. Sacks, A. Mauger, Y. Noat,Supercond. Sci. Technol. 28, 105014 (2015)]. In this work, we calculate thetemperature dependent DOS using this model for different doping levels from underdoped tooverdoped. In all situations, due to the presence of excited pairs, a pseudogap is foundabove T_c while the normal DOSis recovered at T^?, the pair formation temperature. Asimilar behavior is found as a function of magnetic field, crossing a vortex, where apseudogap exists in the vortex core. We show that the precise DOS shape depends oncombined pair (boson) and quasiparticle (fermion) excitations, allowing for a deeperunderstanding of the SC to the PG transition.     

A generalized Uhlenbeck and Beth formula for the third cluster coefficient

Relatively recently (Amaya-Tapia et al., 2011), we presented a formula for the evaluation of the third Bose fugacity coefficient–leading to the third virial coefficient–in terms of three-body eigenphase shifts, for particles subject to repulsive forces. An analytical calculation for a 1-dim. model, for which the result is known, confirmed the validity of this approach. We now extend the formalism to particles with attractive forces, and therefore must allow for the possibility that the particles have bound states. We thus obtain a true generalization of the famous formula of Uhlenbeck and Beth (Uhlenbeck and Beth, 1936; Beth and Uhlenbeck, 1937) and of Gropper (Gropper, 1936, 1937) for the second virial. We illustrate our formalism by a calculation, in an adiabatic approximation, of the third cluster in one dimension, using McGuire’s model as in our previous paper, but with attractive forces. The inclusion of three-body bound states is trivial; taking into account states having asymptotically two particles bound, and one free, is not.     

FDMX: extended X‐ray absorption fine structure calculations using the finite difference method

A new theoretical approach and computational package, FDMX, for general calculations of X‐ray absorption fine structure (XAFS) over an extended energy range within a full‐potential model is presented. The final‐state photoelectron wavefunction is calculated over an energy‐dependent spatial mesh, allowing for a complete representation of all scattering paths. The electronic potentials and corresponding wavefunctions are subject to constraints based on physicality and self‐consistency, allowing for accurate absorption cross sections in the near‐edge region, while higher‐energy results are enabled by the implementation of effective Debye–Waller damping and new implementations of second‐order lifetime broadening. These include inelastic photoelectron scattering and, for the first time, plasmon excitation coupling. This is the first full‐potential package available that can calculate accurate XAFS spectra across a complete energy range within a single framework and without fitted parameters. Example spectra are provided for elemental Sn, rutile TiO₂ and the FeO₆ octahedron.     

Ammonium Acetate Catalyzed Formation of 1,5-Benzodiazepines through [4+2+1] Cycloaddition Involving 5-Hydroxymethylfurfural

The use of the renewable platform molecule 5-hydroxymethylfurfural (5-HMF) in multi-component reaction with a diamine and an alkynone to generate seven-membered 1,5-benzodiazepines is described. Due to the sensitivity of 5-HMF to strong acidic and basic conditions, the investigation required an in-depth revisit of reaction parameters as compared to benchmark aldehydes. Among catalysts/solvents couples, ammonium acetate in ethanol proved to be a clean and efficient system. These optimized conditions were subsequently used to investigate the scope of the reaction providing a library of 1,5-benzodiazepines in moderate to good yields from a wide range of diversely substituted diamines and alkynones or alkyl alkynoates.     

Magnetic Anisotropy Transfer from Mono- to Polymetallic Complexes

The reaction of multi-bidentate oxamate-based copper(II) complexes with the [Ni(ⁱPrtacn)Cl₂] complex (ⁱPrtacn:1,4,7-triisopropyl-1,4,7-triazacyclononane) has been investigated. X-ray diffraction studies reveal that for all compounds the oxamato κO,κΟ’ bidentate coordination site replaces the two chloride ions in [Ni(iPrtacn)Cl₂] to form trimetallic {CuNi₂} ( 1 – 3) , hexametallic {Cu₂Ni₄} ( 4 ) and enneametallic {Cu₃Ni₆} ( 5 ) complexes. The investigation of the magnetic properties shows that Cu−Ni interactions through the oxamato bridge are in the expected range (−111 cm⁻¹, −68 cm⁻¹). For 1 – 3 , both the sign and strength of the magnetic couplings are computed independently from DFT calculations, and these estimates broadly agree with the experiments. The magnetization measurements and EPR studies reveal that 1 – 3 are anisotropic: a significant portion of the large anisotropy of the [Ni(ⁱPrtacn)Cl₂] complex is retained, resulting in a D value for the S=3/2 ground state of 5 cm⁻¹ on average. This is no longer the case for 4 and 5 where the anisotropy of the Ni(II) complexes is diluted due to the high nuclearity of the final edifices. These results show that it is possible to obtain trimetallic complexes with a high anisotropy and a high spin value for the ground state by a judicious choice of the interacting metal ions.     

Carbon-Phosphorus Ligands with Extreme Donating Character

Carbeniophosphines [R₂C⁺−PR₂] and phosphonium ylides [R₃P⁺−CR₂⁻] are two complementary classes of carbon-phosphorus based ligands defined by their unique donor properties. Indeed, while carbeniophosphines are electron-poor P-ligands due to the positioning of a positive charge near the coordinating P-atom, phosphonium ylides are electron-rich C-ligands due to the presence of a negatively charged coordinating C-atom. Based on this knowledge, this account summarizes our recent contribution on these two classes of carbon-phosphorus ligands, and in particular the strategies developed to lower the donor character of carbeniophosphines and enhance that of phosphonium ylides. This led us to design, at both extremities of the donating scale, extremely electron-poor P-ligands exemplified by imidazoliophosphonites [R₂C⁺−P(OR)₂] and dicarbeniophosphines [(R₂C⁺)₂−PR], and extremely electron-rich C-ligands illustrated by pincer architectures exhibiting several phosphonium ylide donor extremities. In the context of carbon-phosphorus analogy, the closely related cases of ligands where the C-atom of a NHC ligand is in close proximity of two positive charges, and that of a phosphonium ylide coordinated through its P-atom are also discussed. An overview of the synthetic methods, coordinating properties, general reactivity and electronic structure of all these C,P-based species is presented here.