Palladium-catalyzed asymmetric allylic alkylation of meso- and dl-1,2-divinylethylene carbonate.
The palladium-catalyzed asymmetric allylic alkylation of a 1:1 mixture of dl- and meso-1,2-divinylethylene carbonate is reported. For the first time, both the ionization and nucleophilic addition steps of the catalytic cycle act as enantiodiscriminating steps to give a single product in high enantiomeric excess. The reactions proceed in >98% ee to efficiently generate useful chiral building blocks from acrolein. The absolute and relative configurations of iso-cladospolide B and 11-epi-iso-cladospolide B were verified by total synthesis, solving an apparent discrepancy in the literature.
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
Barry M
BM
Trost
Aaron
A
Aponick
D000438:Alcohols / Q000138:chemical synthesis; D000478:Alkylation; D000498:Allyl Compounds / Q000138:chemical synthesis*; D002254:Carbonates / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry; D018942:Macrolides / Q000138:chemical synthesis; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D000438:Alcohols; D000498:Allyl Compounds; D002254:Carbonates; D004852:Epoxy Compounds; D018942:Macrolides; D014753:Vinyl Compounds; C492940:cladospolide B; D010165:Palladium