Unexpected deprotection of silyl and THP ethers induced by serious disparity in the quality of Pd/C catalysts and elucidation of the mechanism

Article abstract of DOI:10.1016/j.tet.2004.05.040

Commercial Pd/C catalysts show different catalytic activity toward the deprotection of silyl and THP ethers. The Pd/C purchased from Merck and ACROS exhibits marked tendency to cleave these protective groups unexpectedly without hydrogen conditions although Aldrich's Pd/C (20,569-9) is inactive in the absence of hydrogen. It was proved that the Pd/C disparity toward the deprotection of TES and THP ethers results from residual acids and/or palladium chloride in the production process of Pd/Cs. Although a TES ether cleavage reaction in the absence of hydrogen and a THP ether cleavage reaction in the presence of hydrogen using 10% Pd/C were recently published, we could conclude they were only an acid-catalyzed solvolysis, the acid being released from the catalyst. Hydrogen is essential for the actual 10% Pd/C-catalyzed cleavage of TES ethers and THP ethers which must be stable under the true Pd/C-catalyzed hydrogenation conditions.