Stereochemical requirements for the beta-deuterium isotope effect in the SN1 displacement of vinyl esters

✍ Scribed by D.D. Maness; L.D. Turrentine

• Book ID: 104246698
• Publisher: Elsevier Science
• Year: 1973
• Tongue: French
• Weight: 157 KB
• Volume: 14
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)95703-x

✦ Synopsis

Available evidence(l) indicates that under normal SN~ solvolytlc condltlons a vinyl cation of linear configuration 1s the thermodynamically favored intermediate. The stereochemical course of the reaction path from product-forming intermediate to product is thus described At this time no lnformatlon is available on the stereochemistry of the first-formed intermediate (be it the same as the product-forming one or not) or of the transltlon state. Therefore the stereocnemlcal course leading from vinyl reactant to the oroduct-forming intermediate has not been resolved. Examination of this sequence would add much to the basic knowledge and understanding of these lnterestlng, reactive intermediates. Rate constants involving hyperconJugatlve effects are quite sensitive to transition state stereochemlstry.(2) The maximum s-deutenum isotope effect 1s observed ln SNI solvolyses of sat-