Base-catalyzed Rearrangement Reactions of 4a-Ammomethyl-1,2,3,4,4a,9-Hexahydrophenanthrenes. Synthesis of D-Normorphinans

The syntheses of members of the D-normorphinan system, which is unreported prior to this work, are described. Two methods employing 4a-aminomethyl-1,2,3,4,4a,9-hexahydrophenan-threnes (1a-d) as starting materials were developed. These were the base-catalyzed rearrangement of 1 to the 4a-aminomethyl-4a,10a-cis-1,2,3,4,4a,10a-hexahydrophenanthrenes 2 followed by base-catalyzed ring closure of one of these (2b) to N-methyl-D-normorphinan (3) and the intramolecular cyclization of the chloramine derived from 2c to give 10-substituted-N-benzyl-D-normorphinans which were transformed into a number of derivatives.The Eu(fod)3 induced shifts in the n.m.r. spectra of certain of these D-normorphinans are reported and form the basis of a configurational assignment to one of the products obtained on chloramine solvolysis.