Formation of the products of [1+2]- and [2+2]-cycloaddition in the catalytic reaction of cyclopropenes with unsaturated polycyclic hydrocarbons

Autor: Tomilov, Yu. V., Tsvetkova, N. M., Nefedov, O. M.
Zdroj: Russian Chemical Bulletin; July 1989, Vol. 38 Issue: 7 p1456-1465, 10p
Abstrakt: 1.The reaction of 3,3-disubstituted cyclopropene hydrocarbons with norbornadiene in the presence of 1–3 mole % CuCl or (PhO)3P·CuCl at 0–40‡C takes place according to the scheme of both [2 + 2]- and [1 + 2]- cycloaddition with the formation of the corresponding exo,trans-tetracyclo[5.2.1.02, 6.03, 5]-8-decenes and 3-vinykltricyclo[3.2.1.02, 4]-6-octenes with a total yield of 70–90%, and the yield of the latter increased with an increase in the temperature in going from (PhO)3P·CuCl to CuCl.2.The reaction of 3-methyl-3-cyclopropylcyclopropene with more complex polycyclic hydrocarbons containing a bicyclo[2.2.1]heptene fragment takes place less efficiently and less selectively than with norbornene, and yields a mixture of products of [1+2]- and [2+2]-cycloaddition with a yield of 30–65% and significant dimerization of the starting cyclopropene in the presence of (PhO)3P·CuCl even at -20‡C.
Databáze: Supplemental Index
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