Heteroatom-directed reverse Wacker oxidations. Synthesis of the reported structure of (-)-herbaric acid.
A microwave-assisted chemoenzymatic resolution has been used to install the C3 stereocenter of the reported structure of the fungal metabolite herbaric acid in high enantiomeric excess. The synthesis and stereochemical assignment was accomplished using a completely regioselective anti-Markovnikov addition of water to vinylphthalide 3, achieved using a heteroatom-directed Wacker oxidation that proceeds with retention of stereochemistry. These results establish that so-called "reverse" Wacker oxidations are a viable alternative to hydroboration/oxidation procedures.
Choi
Peter J
PJ
Department of Chemistry, University of Auckland, 23 Symonds St., Auckland, New Zealand.
Sperry
Jonathan
J
Brimble
Margaret A
MA
D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D005658:Fungi / Q000378:metabolism; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013379:Substrate Specificity
D001688:Biological Products; D006574:Heterocyclic Compounds, 2-Ring; D007783:Lactones; C555738:herbaric acid