Oxidative functionalization of unactivated carbon-hydrogen bonds in heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (HCTD)

Article abstract of DOI:10.1016/S0040-4020(96)01110-6

Gif-type reactions have been used to perform direct oxidative functionalization of the title compound (HCTD, 1). Thus, GoAgg(III) and GoAgg(IV) promoted oxidations of 1 afford 1-(2' -pyridyl)heptacyclo[6.6.0.0^2,6.0^3,13.0^4,11.0^5,9.0^10,14]tetra decane [i.e., 1-(2'-pyridyl)HCTD, 2] in 6-10% isolated yield. In addition to 2, GoAgg(V) promoted oxidation of 1 produced heptacyclo[6.6.6.0.0^2,6.0^3,13.0^4,11.0^5,9.0^10,14]tetradecan-7 -one (HCTD-7-one, 3) and 1-(4'-pyridyl)HCTD (4) in low isolated yield. Finally, oxidation of 1 performed by using an Fe(II)-t-BuOOH system afforded several products, including [6.6.0,0^2,6.0^3,13.0^4,11.0^5,9]tetradecane- 10,14-dione (6) and 14-hydroxyhexacyclo[6.6.0,0^2,6.0^3,13.0^4,11.0^5,9]-teradecan-10-one (7), both of which resulted via oxidative cleavage of the C(1)-C(2) σ-bond in 1.