Zirconocene-mediated route to enantiopure 9-oxabicyclononanes functionalized on both carbon bridges

[reaction: see text] A zirconocene-mediated ring contraction of 4-vinylfuranosides generated either from d-arabinose or d-glucose is followed by sequential oxidation to the ketone and alkynyl Grignard addition. The resulting cis-cyclobutanediols are subjected in turn to thermal rearrangement and intramolecular oxymercuration-demercuration. The regiochemistry of the final ring closure is controlled by the nature of R.     

Synthesis of 4-acetylisocoumarin: first total syntheses of AGI-7 and sescandelin

A practical synthetic route to 4-acetylisocoumarins and the first total synthesis of AGI-7 (5) and sescandelin (4) are described. The readily available homophthalate 8 was transformed to the vinylogous amide ester 13 in high overall yield. Upon treatment of 13 with refluxing aqueous formic acid, the desired 4-acetylisocoumarin (5) and its regioisomer 3-methyl-4-formylisocoumarin (17) were produced in a 3:1 ratio. After separation of the desired product (5) from the unwanted minor isomer, the enantioselective reduction of AGI-7 by borane in the presence of Corey's (S)-oxazaborolidine reagent afforded (+)-sescandelin (4) with a 93% ee.     

Isolation of essential oils from tobacco by gas co-distillation/solvent extraction

Summary The essential oils have been isolated from tobacco leaves using a simple gas co-distillation apparatus. The method involves co-distillation with water under the continuous stream of an inert gas with subsequent single solvent extraction of the distillate. The extract is analysed on GC and GC/MS in splitless injection mode without further concentration. The method was evaluated for reproducibility using n-octadecane as an internal standard. The distillation-extraction procedure was reporducible with an average deviation of ±3% for the major constituents. The present method was applied to the analyses of the essential oils of other agricultural products.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday.