Synthetic studies on the ingenane diterpenes. An improved entry into a trans-intrabridgehead system.
[reaction: see text] The efficient construction of an ingenol intermediate exhibiting "insideminus signoutside" intrabridgehead stereochemistry is reported. The sequence features the net conversion of a cis-intrabridgehead compound into a highly strained trans-species via palladium-mediated isomerization of an allylic epoxide followed by a low-temperature alkoxide-accelerated 1,5-hydrogen migration.
Rigby
James H
JH
Department of Chemistry, Wayne State University, Detroit, Michigan 48202-3489, USA. jhr@chem.wayne.edu
Bazin
Bérangère
B
Meyer
J Hoyt
JH
Mohammadi
Farahnaz
F
D001952:Bridged-Ring Compounds; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
D001952:Bridged-Ring Compounds; D004224:Diterpenes; D004852:Epoxy Compounds; D010165:Palladium; C008125:ingenol