Parviflorine,a glycosidic spirobenzylisoquinoline alkaloid

(+)-Parviflorine ($\text{1}$), found in $\text{Fumaria parviflora}$ Lam. (Fumariaceae), is the first known glycosidic spirobenzylisoquinoline alkaloid. Its acid hydrolysis yields (+)-parfumine ($\text{4}$) and D-glucose. Klyne's rule indicates that $\text{1}$ is a β-D-glucoside. The absolute configuration shown in expressions $\text{1-11}$ is predominant among spirobenzylisoquinolines. A generalization has been drawn between plant source and the oxygenation pattern of ring C for the spirobenzylisoquinoline alkaloids.     

Proton magnetic resonance spectra of substituted adamantane-2,4-diones. Determination of the C-6 and C-9 stereochemistry

The 220 MHz ¹H NMR spectra of 6-hydroxy-7-methyl-6-phenyladamantane-2,4-dione, 6-hydroxy-5,7-dimethyl-6-phenyladamantane-2,4-dione, and 6-hydroxy-7,9-dimethyl-6-phenyladamantane-2,4-dione have been determined and complete proton assignments carried out with the aid of multiple irradiation. The stereochemistry of the C-6 and C-9 chiral centres have been determined and some of the factors affecting the magnitude of the geminal, vicinal and W coupling constants are discussed.     

Hyperpolarization of 13C through order transfer from parahydrogen: a new contrast agent for MRI

The order within proton pairs in organic molecules, resulting from hydrogenation with parahydrogen, can be transferred in great part to nearby carbon 13 spins through adequate field manipulations. The molecules with hyperpolarized 13C thus obtained can be used as new contrast agents of high efficiency in MRI. After a brief presentation of the hydrogenation process and apparatus, in relatively low magnetic field, we describe the procedure of order transfer to the 13C spins through a sudden drop from the initial field to zero field followed by an adiabatic remagnetization. The expected final polarizations in the absence of relaxation are given for several compounds. Finally, we show an example of MR images observed in vivo on animals as an illustration of the contrast capacity of this new method.     

Mechanistic studies of the transfer dehydrogenation of cyclooctane catalyzed by iridium bis(phosphinite) p-XPCP pincer complexes

Reaction of bis(phosphinite) PCP iridium pincer complexes (p-XPCP)IrHCl (5a-f) [X = MeO (5a), Me (5b), H (5c), F (5d), C(6)F(5) (5e), Ar(F)(= 3,5-bis(trifluoromethyl)phenyl) (5f)] with NaOtBu in neat cyclooctane (COA) generates 1:1 mixtures of the respective (p-XPCP)IrH(2) complexes 4a-f and the cyclooctene (COE) olefin complexes (p-XPCP)Ir(COE) (6a-f) at 23 degrees C. At higher temperatures, complexes 4 and 6 are equilibrated because of the degenerate transfer dehydrogenation of COA with free COE (6 + COA right harpoon over left harpoon 4 + 2COE), as was shown by temperature-dependent equilibrium constants and spin saturation transfer experiments at 80 degrees C. At this temperature, the COE complexes 6 exchange with free COE on the NMR time scale with the more electron-deficient complexes 6 exchanging COE faster. The exchange is dissociative and zero order in [COE]. Further analysis reveals that the stoichiometric hydrogenation of COE by complex 4f, and thus the separated back reaction 4f + 2COE --> 6f + COA proceeds at temperatures as low as -100 degrees C with the intermediacy of two isomeric complexes (p-Ar(F)PCP)Ir(H)(2)(COE) (8f, 8f'). COE deuteration with the perdeuterated complex 4f-d(38) at -100 degrees C results in hydrogen incorporation into the hydridic sites of complexes 8f,8f'-d(38) but not in the hydridic sites of complex 4f-d(38), thus rendering COE migratory insertion in complexes 8f,8f' reversible and COE coordination by complex 4f rate-determining for the overall COE deuteration.     

Weighted allocation rules for standard fixed tree games

In this paper we consider standard fixed tree games, for which each vertex unequal to the root is inhabited by exactly one player. We present two weighted allocation rules, the weighted down-home allocation and the weighted neighbour-home allocation, both inspired by the painting story in Maschler et al. (1995) . We show, in a constructive way, that the core equals both the set of weighted down-home allocations and the set of weighted neighbour allocations. Since every weighted down-home allocation specifies a weighted Shapley value (Kalai and Samet (1988)) in a natural way, and vice versa, our results provide an alternative proof of the fact that the core of a standard fixed tree game equals the set of weighted Shapley values. The class of weighted neighbour allocations is a generalization of the nucleolus, in the sense that the latter is in this class as the special member where players have all equal weights.     

Adjustable cavity for host-guest recognition in cofacial bis-porphyrinic tweezer

The synthesis of a cofacial bis-porphyrinic tweezer bearing a tris-anthracenic spacer is reported. Its behavior as host has been evidenced as well as the ability of its cavity to adjust to guests of various sizes.     

A supramolecular cup-and-ball C60-porphyrin conjugate system

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.     

Donor-substituted peralkynylated "radiaannulenes": novel all-carbon macrocycles with an intense intramolecular charge-transfer

A novel class of planar, highly conjugated all-carbon macrocycles, which we christened "radiaannulenes", have been prepared based on acetylenic scaffolding using tetraethynylethene (TEE) building blocks; these structures are powerful electron acceptors and, upon peripheral substitution with electron-donating N,N-dialkylanilino groups, display intense intramolecular charge-transfer.