Selective 1,5-alkylidenecarbene insertion reactions on [3.2.1] oxabicyclic ethers: a new approach toward the AB ring system of ingenol.
Two methods to achieve the formal aldol reaction between acetone and two oxabicyclic [3.2.1] ketones are reported. The trimethylsilyl-protected beta-hydroxy ketones are converted by a Wittig reaction into vinyl chlorides as synthetic precursors to alkylidenecarbenes. Selective 1,5 C-H over 1,5 O-Si insertion has been applied to the synthesis of a model for the ABC ring system of ingenol.
Grainger
Richard S
RS
Department of Chemistry, King's College London, Strand, London WC2R 2LS. richard.grainger@kcl.ac.uk
Owoare
Richard B
RB
D002384:Catalysis; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D004988:Ethers, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
D004224:Diterpenes; D004988:Ethers, Cyclic; C008125:ingenol