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

1.

The reaction of 3,3-disubstituted cyclopropene hydrocarbons with norbornadiene in the presence of 1–3 mole % CuCl or (PhO)3P·CuCl at 0–40C 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 –20C.

For previous communication, see [1].