The synthesis of 3-Oxatetracyclo[5,3,1,1^2,6,0^4,9]dodecane (oxaiceane) and 12-Oxatetracyclo[5,3,1,1^2,5,0^4,9]dodecane (abeo-oxaiceane) and the reduction of intermediate mercury compounds

Abstract

Tricyclo[5,3,1,0^4,9]undec-5-en-2-one (2) was reduced by sodium borohydride to the endo alcohol (3). Oxymercuration-reduction gave a mixture of oxaiceane (4) and abeo-oxaiceane (5) and these were separated and characterized. The intermediate mercury compound, which leads on reduction to oxaiceane, was obtained pure and it was shown that the mercury group is in the hindered prow (flagpole) position. The reaction which allowed this determination was the sodium amalgam- deuterium oxide reduction of the mercury compound which proceeds with retention of configuration. This is probably the most demanding test to which the stereospecificity of this reaction has yet been put.