Abstract
Hydroboration of Δ8-desoxycodeine (I) gave a B/C trans-fused morphine derivative, (-)-3-methoxy-8α-hydroxy-4, 5α-oxy-N-methylisomorphinan (III) along with two minor products, dihydropseudocodeine (IV) and VII. III, by reaction with p-toluenesulfonyl-chloride gave the 8-p-toluenesulfonate (Vc), which was treated with lithiun aluminum hydride to give (-)-3-methoxy-4, 5α-oxy-N-methylisomorphinan (VII). Elimination reaction of Vc with 2, 4, 6-collidine afforded two double-bond isomers, I and 3-methoxy-4, 5α-oxy-Δ7-N-methylisomorphinan (XII). I gave on hydrogenation the known dihydrodesoxycodeine (XIII). Hydrogenation of XII gave the B/C trans isomer, VII. Some additional studies were made on the hydroboration product (III) and its derivatives to support the B/C trans pentacyclic structure.
