Degenerate cope rearrangement of tetracyclo[7.3.1.02(')8.04(')12]trideca-5,10-diene

Article abstract of DOI:10.1016/S0040-4020(97)00335-9

Tetracyclo[7 3 1.0²(')⁸.0^4,12]trideca-5,10-diene (3) is synthesized and partially resolved via reversible ligand exchange in its ⁴η-diene-tfacac-rhodium(I) complexes 10 and 11 with the C₂-chiral bidentate bis-[4(R)-methyl-5(R)-phenyloxazolinyl]methanide anion. The Cope rearrangment of (+) 3, converting it into its mirror image, is measured between 39-57°C. The kinetic parameters show that the rate of this rearrangement is 10⁸ times faster than that of the parent hexa-1,5-diene. The strain and rigidity of the cage compound 3 provide an explanation.