CHEMOSPECIFIC DEUTERATION OF PROSTAGLANDIN SILYL ETHERS

Complete chemical selectivity (i.e., chemospecificity) has been achieved in the homogeneous deuteration of C5C6 and endocyclic C10C11 prostaglandin double bonds without rearrangement or partial reduction of C13C14 or C8C12 double bonds. The homogeneous deuteration reaction utilizes protection of the C13C14 double bond as the C15 O-silyl ether and protection of the carboxyl group as the methyl ester prior to reduction under molecular deuterium with tris(triphenylphosphine)chlororhodium (I) (Wilkinson's catalyst) in 60:40 acetone:benzene at 25°C. The reaction has been used to prepare six specifically deuterated prostaglandins: 5,6-dideuterio-PGF1α, 5,6-dideuterio-PGE1, 5,6-dideuterio-PGB1, 3,3,4,4,5,6-hexadeuterio-PGF1α, 5,6,10,11-tetradeuterio-11-deoxy-PGE1, and 10,11-dideuterio-11-deoxy-PGE1. © 1979.