T. Mitsudo, Toshiaki Suzuki, Shiwei Zhang
Feb 19, 1999
Citations
0
Influential Citations
47
Citations
Journal
Journal of the American Chemical Society
Abstract
Bicyclo[2.2.1]hepta-2,5-diene (2,5-norbornadiene) dimerizes in the presence of a catalytic amount of Ru(1-2:5-6-η-cyclooctadiene)(1-6-η-cyclooctatriene) (Ru(cod)(cot)) and an electron-deficient olefin such as N,N-dimethylacrylamide, dimethyl fumarate, or dimethyl maleate in toluene or tetrahydrofuran (THF) to give a new compound, pentacyclo[6.6.0.02,6.03,13.010,14]tetradeca-4,11-diene (PCTD), in high yield along with a small amount of a known endo−endo dimer, heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (HCTD), which is a major product in the reaction in DMSO. Ru(cod)(cot)-dimethyl fumarate in THF was the most efficient catalyst, and the yield of PCTD was 96% even at 40 °C. The structure of PCTD was determined by X-ray analysis of its derivative, [AgOTf(PCTD)]n. PCTD was found to be derived via endo−endo dimerization of 2,5-norbornadiene. Formation of PCTD from two molecules of 2,5-norbornadiene involves the cleavage of two carbon−carbon bonds. Dimerization of 7-tert-butoxy-2,5-norbornadiene ...