A molecular orbital and crystallographic study of the structure and p-facial regioselectivity of 9-chloro-1,4,5,8-tetrahydro-4a,8a-methanonaphthalene.
In: Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), (1992) ; Nr. 4, S. 447-448
Zeitschriftenaufsatz / Fach: Chemie
The title compd. 1 undergoes reaction with electrophilic reagents such as dichlorocarbene regioselectively on the p-face endo to the chlorine. The crystal structure of 1 indicates significant geometrical distortions of the two rings, which are attributed to a stabilizing interaction between the C-Cl s* orbital and the exo p-orbital. PM3 calcns. of these orbitals, the electrostatic potential and transition state models for dichlorocarbene addn. all agree with the obsd. regioselectivity.