Journal of the Chemical Society. Perkin transactions I p. 1549 - 1556 (1981)
Update date:2022-07-30
Topics:
Fleming, Ian
Michael, Joseph P.
As part of a projected synthesis of gelsemine (1), the synthesis of dimethyl 7-oxobicyclo<2.2.1>hept-5-ene-2-endo,3-exo-dicarboxylate (5) is described.The route involves the silicon-controlled rearrangement of 5-exo-bromo-3-exo-methoxycarbonyl-7-anti-trimethylsilylbicyclo<2.2.1>heptane-2,6-carbolactone (9), catalysed by silver ions in methanol, to give dimethyl 7-syn-hydroxybicyclo<2.2.1>hept-5-ene-2-endo,3-exo-dicarboxylate (11).Some related reactions show that a 7-trimethylsilyl group in a norbornene can be used to synthesise other 7-functionalised norbornenes.Thus the epoxide (13) of methyl 7-anty-trimethylsilylbicyclo<2.2.1>hept-5-ene-2-endo-carboxylate (12) rearranges on treatment with boron trifluoride-ether to give methyl 7-anti-hydroxybicyclo<2.2.1>hept-5-ene-2-exo-carboxylate (14), and treatment of (12) with bromine gives mainly the rearranged bromide, methyl 7-anti-bromobicyclo<2.2.1>hept-5-ene-2-exo-carboxylate (16).Some limitations in this approach to 7-functionalised norbornenes are also described.
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