Chemospecific deuteration of prostaglandin silyl ethers

Complete chemical selectivity (, chemospecificity) has been achieved in the homogeneous deuteration of C₅---C₆ and endocyclic C₁₀---C₁₁ prostaglandin double bonds without rearrangement or partial reduction of C₁₃---C₁₄ or C₈---C₁₂ double bonds. The homogeneous deuteration reaction utilizes protection of the C₁₃---C₁₄ 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-PGF_1α, 5,6-dideuterio-PGE₁, 5,6-dideuterio-PGB₁, 3,3,4,4,5,6-hexadeuterio-PGF_1α, 5,6,10,11-tetradeuterio-11-deoxy-PGE₁, and 10,11-dideuterio-11-deoxy-PGE₁.