THE ORIENTATION OF SUBSTITUTION IN METALLATION OF DIMETHYLAMINOMETHYL-, HYDROXYMETHYL- AND DIPHENYLPHOSPHIONO-CYMANTRENES

Article abstract of DOI:10.1016/S0022-328X(00)93594-0

Dimethylaminomethyl- and hydroxymethyl-cymantrenes, when treated with n-butyllithium, are selectively metallated in the 2(5) position of the Cp ringand are converted into 1,2-disubstituted derivatives of cymantrene by subsequent treatment with electrophilic reagents.Similar reactions in the case of diphenylphosphinocymantrene result in a selective preparation of 1,3-disubstituted derivatives.The metallation orientation is established by chemical methods and NMR-LIS (lanthanide-induced shift) techniques.A full assignment of signals in the PMR and 13C NMR spectra of the studied monosubstituted cymantrene derivatives has been effected.