Strained tridecane cage systems

Hexacyclo6.5.0.0^2,7.0^4,12.0^5,10.0^9.13]tridecane (HCTD) contains two four-membered, two five-membered and two six-membered rings fused into a cage structure which contains about 77.0 kcal/mol of strain energy. Attempts to prepare the thioketal from the diketone of HCTD led to a skeletal rearrangement to produce a cage with one four-membered, four five-membered, and two six-membered rings fused into a cage (RHCTD). The corresponding RHCTD hydrocarbon has a strain energy 13.7 kcal/mol less than that of the starting tridecane (HCTD) which provides the driving force for the rearrangement. The X-ray structures of two HCTD derivatives and one RHCTD derivative are reported. The bond lengths in the three reported structures are normal for cages of this type. The structure of tetracyclo6.3.0.0^3,7.0^4,11]undecane-5,10-dione mono(ketene 1,3-propanedithioacetal) is discussed also.