| Title: | "Tandem reduction-chloroallylboration of esters: asymmetric synthesis of lamoxirene, the spermatozoid releasing and attracting pheromone of the laminariales (Phaeophyceae)" |
| Address: | "Max-Planck-Institute for Chemical Ecology, Jena, Germany" |
| ISSN/ISBN: | 0022-3263 (Print) 0022-3263 (Linking) |
| Abstract: | "The asymmetric synthesis of all four stereoisomers of lamoxirene (cis-2-cyclohepta-2,5-dienyl-3-vinyloxirane), the spermatozoid-releasing and -attracting pheromone of the Laminariales (Phaeophyceae), is reported. Chiral ethyl cyclohepta-2,5-diene carboxylates, prepared by a divinylcyclopropane Cope rearrangement, were effectively alkylated by means of a novel tandem DIBAL-H reduction/asymmetric alpha-chloroallylboration using (Z)-gamma-chloroallyldiisopinocampheylboranes. The ensuing syn-alpha-chlorohydrins were transformed into the corresponding vinyloxiranes with DBU, providing all four isomers of the pheromone in good chemical and excellent optical yield (90-97% ee). Spermatozoid-release assays were conducted with the sympatrically growing species L. digitata, L. hyperborea, and L. saccharina and established (1'S,2R,3S)-1c as the most active isomer in all cases" |
| Keywords: | Alkylation Allyl Compounds/chemical synthesis Carboxylic Acids/chemical synthesis Cyclization Germ Cells/*drug effects Laminaria/*metabolism Pheromones/*chemical synthesis/chemistry/pharmacology Seawater Signal Transduction Stereoisomerism Structure-Activ; |
| Notes: | "MedlineHertweck, C Boland, W eng Research Support, Non-U.S. Gov't 2000/05/02 J Org Chem. 2000 Apr 21; 65(8):2458-63. doi: 10.1021/jo991629r" |
