Rearrangement of 5-trimethylsilylthebaine on treatment with L-selectride: an efficient synthesis of (+)-bractazonine

Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine with strong Lewis acids is known to lead to a similar rearrangement through migration of the alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However, for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the beta-silyl effect dominates in the stabilization of any positive charge. This rearrangement provides a clear example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides an efficient synthesis of (+)-bractazonine from thebaine.     

Reactivity of stable trifluoroacetaldehyde hemiaminals. 2. Generation and synthetic potentialities of fluorinated iminiums

Under Lewis acid activation, hemiaminals of trifluoroacetaldehyde and related (fluoroalkyl)aldehydes generate iminium species that can react with various nucleophiles to provide fluorinated amines.     

The complex of a bivalent derivative of galanthamine with torpedo acetylcholinesterase displays drastic deformation of the active-site gorge: implications for structure-based drug design

Bifunctional derivatives of the alkaloid galanthamine, designed to interact with both the active site of the enzyme acetylcholinesterase (AChE) and its peripheral cation binding site, have been assayed with Torpedo californica AChE (TcAChE), and the three-dimensional structures of their complexes with the enzyme have been solved by X-ray crystallography. Differences were noted between the IC(50) values obtained for TcAChE and those for Electrophorus electricus AChE. These differences are ascribed to sequence differences in one or two residues lining the active-site gorge of the enzyme. The binding of one of the inhibitors disrupts the native conformation of one wall of the gorge, formed by the loop Trp279-Phe290. It is proposed that flexibility of this loop may permit the binding of inhibitors such as galanthamine, which are too bulky to penetrate the narrow neck of the gorge formed by Tyr121 and Phe330 as seen in the crystal structure.     

Vitamin D: a concise synthesis of the C19 hydroxylated enyne A-ring, an interesting precursor for the preparation of C19 substituted vitamin D analogues

A new C₁₉ hydroxylated enyne 15, as potential A-ring building block of vitamin D analogues, was synthesized in enantiomerically pure form in nine steps from (−)-(S)-limonene. This short synthesis involved ozonolyzis of 1,2-limonene oxide followed by a Criegee rearrangement, epoxide trans diaxial ring opening by lithium acetylide, elimination, epoxidation and syn β-elimination of the resulting homopropargylic oxirane.     

A mechanistic investigation of the carbon-carbon bond cleavage of aryl and alkyl cyanides using a cationic RhIII silyl complex

Cationic Rh(III) complex [Cp(PMe(3))Rh(SiPh(3))(CH(2)Cl(2))]BAr(4)' (1) activates the carbon-carbon bond of aryl and alkyl cyanides (R-CN, where R = Ph, (4-(CF(3))C(6)H(4)), (4-(OMe)C(6)H(4)), Me, (i)Pr, (t)Bu) to produce complexes of the general formula [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'. With the exception of the (t)BuCN case, every reaction proceeds at room temperature (t(1/2) < 1 h for aryl cyanides, t(1/2) < 14 h for alkyl cyanides). A general mechanism is presented on the basis of (1) an X-ray crystal structure determination of an intermediate isolated from the reaction involving 4-methoxybenzonitrile and (2) kinetic studies performed on the C-C bond cleavage of para-substituted aryl cyanides. Initial formation of an eta(1)-nitrile species is observed, followed by conversion to an eta(2)-iminoacyl intermediate, which was observed to undergo migration of R (aryl or alkyl) to rhodium to form the product [Cp*(PMe(3))Rh(R)(CNSiPh(3))]BAr(4)'.     

Studies of the reaction of substituted 1,2-dithiole-3-thiones and -3-ones with sodium cyanide in acetonitrile

The reactions of substituted 1,2-dithiole-3-thiones and -3-ones with sodium cyanide, in acetonitrile, afford convenient routes to indolizine, pyrrolo[1,2-a]pyrazine and 4H-1,3-thiazin-4-one species.     

Conversion directe des phospholes en dihydro-6,7 phosphepines dans la sphere de coordination du tungstene

In the presence of AlCl₃, [1-β-chloroethyl-3,4-dimethylphosphole]pentacarbonyltungsten($\text{1}$) rearranges into [1-chloro-3,4-dimethyl-6,7-dihydrophosphepin]pentacarbonyltungsten ($\text{3}$).     

Determination de la structure de perfluoroalcenes a chaines longues par R.M.N. du19F : lère Partie : pefluoroalcenes-1

After a review of 1-perfluoroalkene R_FCFCF₂ synthesis, with R_FC₄F₉, C₅F₁₁, C₆F₁₃, we have studied their fine structures by ¹⁹F N.M.R. This study has led us to first generalize the rules set for the chemical shifts and coupling constants of olefinic fluorine atoms of fluoropropene and their derivatives. Then, we have been able to determinate unambiguously the chemical shifts of the difluoromethylene groups of the perfluorinated chains. We have thus shown, by irradiation, that inversions may take place in the chemical shifts of the CF₂ groups at the β and γ position of the double bond.     

STRUCTURE OF DYE AGGREGATES AND THE MECHANISM(S) OF PHOTOSENSITIZATION OF AgBr*,†

Abstract— This paper reports the present conclusions of an extended investigation on photo-sensitization of silver bromide. A general molecular packing structure for dye aggregates on the AgBr (111) surface is proposed. This structure, along with the observed spectral absorption displacements of small aggregates, is used to elucidate the phenomena of antisensitization and supersensitization. Supersensitization is seen as a partitioning of large dye aggregates into small aggregates by a deliberately added second component or by gaps between the aggregates. This partitioning isolates antisensitizing dye in a small fraction of the aggregates and minimizes its effect. The smallest aggregates are least likely to contain an antisensitizer, and show the highest quantum efficiency for photoconductivity and photographic action. Photoconductivity measurements establish that supersensitization occurs before the electron appears in the AgBr phase.
The question of direct electron injection vs. energy transfer as mechanisms for AgBr photosensitization is examined in terms of radiationless transfer to surface Ag₂S on AgBr. The absorption of surface Ag₂S is shown to be adequate for acceptance of Förster transfer from the dye, and surface Ag₂S is known to be photographically active. However, this mechanism is inefficient, and inadequate to account for observed high efficiency infrared sensitization. Direct electron injection is seen as the more probable mechanism for efficient dye sensitization of AgBr.