7-Methylenequadricyclane, radical cation

Other systems studied include the spiroheptadiene system (13) in which the cyclopropane moiety lies in the nodal plane of the butadiene HOMO [1 2,9 10]bis-methano[2.2]paracyclophane (15), in which two cyclopropane moieties are joined with two benzene rings in such a way that tertiary-tertiary cyclopropane bonds lie parallel to the aromatic n system 7-methylenequadricyclane radical cation (16 ), in which a pair of cyclopropane groups lie orthogonal to an olefinic moiety and the 7-spirocyclopropanenorbomadiene radical cation (18 ), in which a pair of nonconjugated ethene groups and a cyclopropane moiety are joined. 

Electron transfer-induced nucleophilic addition to several otho cyclopropane compounds was also studied. The nucleophilic addition of methanol to quadricy-clane radical cation 8 produces the two methanol adducts 53 and 54. The stereochemistry of the methoxy groups in these structures identifies the preferred direction of nucleophilic attack upon the intermediate radical cations 8. Detailed NOE experiments delineate the structure of 53 and establish conclusively that the norbomene derivative 54 contains a 7-fl ri-methoxy group. The stereochemistry of both is compatible with stereospecific nucleophilic attack exclusively firom the exo-position. 7-Methylenequadricyclane also is attacked exclusively from the exo-face.These results can be explained via backside attack with inversion of configuration. 

---