Stereochimie de la reaction de rupture par le brome de la liaision siliciumaryle du dimethyl-1,2 phenyl-1 silacyclopentane

Stereospecific synthesis of geometric isomers of 1,2-dimethyl-1-phenylsilacyclopentane is described. We demonstrate that brominolysis of the arylsilicon bond occurs with predominant inversion of configuration at the silicon atom of the silacyclopentane ring.     

Etudes stereochimiques dans la serie du silacyclopentane: synthese de dimethyl-1,2 alcoxy-1 silacyclopentanes a stereoisomere preferentiel

The stereoselective alcoholysis of 1,2-dimethyl-1-chlorosilacyclopentane and the catalytic alcoholysis of 1,2-dimethylsilacyclopentane are described.     

Hétérocycles contenant du phosphore. XXXII. Etude de l'action des phosphorhydrazides sur les orthoesters,l'anhydride acétique et l'acide formique

The reaction of phosphodi- or trihydrazides with orthoesters affords mainly 2,3,4,5-tetrahydro-1,2,4,5,3-tetrazaphosphorines and sometimes 4-amino-1,2,4,3-triazaphospholidines. These 1,2,4,5,3-tetrazaphosphorines present a prototropy which explains different pathways of the reaction of these derivatives with formaldehyde or acetone, The structure of all heterocycles which were obtained was established by nmr spectra.     

Alcoyl-gluco-alcaloides: nouveaux composes isoles de pauridiantha lyalii brem (rubiacees)

La structure destrans fe´ruloyl-6′ ettrans sinapoyl-6′ lyaloside, isole´s des feuilles dePauridiantha Lyalii, ae´te´de´termine´e par de´gradation chimique et par spectroscopie (Masse, RMN¹H et¹³C). Ces compose´s font partie d'un groupe structural caracte´rise´par un enchai?nement alcaloide-monoterpe`ne-ose-acide (C<sub>6</sub>-C<sub>3</sub>), groupe dont un seul repre´sentant semble avoire´te´isole´jusqu'a`pre´sent. Leur fonction dans le ve´ge´tal est discute´e.     

Chiral phosphorus ligands for the asymmetric conjugate addition of organocopper reagents

The asymmetric conjugate addition of medium order alkyl cuprate reagents. R₅Cu₃Li₂, to 2-cyclohexen-1-one. 2-cyclopenten-1-one and 2-cyctohepten-1-one, with the help of phosphorus ligand B^*, is described. 3-Alkyl substituted cyclohexanones are obtained in essentially optically pure form. The same chiral ligand, associated with CuI, in catalylic amount (10%), allows the asymmetric conjugate addition of Et₂Zn to 2-cyclohexen-1-one.