The synthesis and structure of 10,11-bistrifluoromethyl-i,o-bicyclo[7.2.2]trideca-10,12-diene. A highly strained inside-outside bicycloalkane derivative.

In/Out Isomerism

“…113 Further oxidation of these radical cations leads to propellanes, with a full 2-electron bond between the bridgehead atoms. Structures were also obtained for the radical cations of N,N′-trimethylene-syn-1,6;8,13-diimino [14]annulene (45) 114 and N,N′-tetramethylene-syn-1,6;8,-13-diimino [14]annulene (46). 68 ESR and ENDOR studies of these species have been carried out, 115,116 and a good correlation of the hyperfine coupling constant a N with the average C-N-C angle established.…”

“…Gassman and co-workers prepared a series of derivatives of in,out -bicyclo[ n .2.2]alkanes ( n = 5−8) through Diels−Alder reactions of cis,trans -1,3-cycloalkadienes. ,,− Few molecular mechanics calculations on these systems have been reported, and the in,out -isomers may be thermodynamically preferred for the larger systems, but it is plain that the in,out -isomers with n = 5 or 6 are severely strained. This is shown by some extremely large C−C−C angles in these compounds.…”