Why would ethanol or water give poor yields in a peptide deprotection hydrogenolysis?
Answers
The following reaction was carried out using ethanol or water as solvents, but gave poor yields in both cases. Suggest why this might be the case and how these problems could be overcome.
I've gathered that this is the deprotection step of a dipeptide synthesis reaction (Phe-Ser). The palladium catalyst and hydrogen gas remove the Cbz group from the n-terminal and the benzyl ester from the c-terminal, with a carbamic acid intermediate that spontaneously decarboxylates to the product.
I don't really understand why ethanol or water would give poor yields as a solvent, since I've seen multiple references where they use exactly those as solvents for this reaction (or methanol, or THF). The only hint I could find was a suggestion that using acetic acid may be necessary when deprotecting a Cbz group from an amine, since protonating the nitrogen facilitates the reaction. A couple of references said that an aliphatic amine could poison the catalyst and require the addition of dilute acid to protonate the amine...I'm lost on why or how the poisoning occurs.
A nudge in the right direction would be greatly appreciated.
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The following reaction was carried out using ethanol or water as solvents, but gave poor yields in both cases. Suggest why this might be the case and how these problems could be overcome.
Deprotection hydrogenolysis
I've gathered that this is the deprotection step of a dipeptide synthesis reaction (Phe-Ser). The palladium catalyst and hydrogen gas remove the Cbz group from the n-terminal and the benzyl ester from the c-terminal, with a carbamic acid intermediate that spontaneously decarboxylates to the product.
I don't really understand why ethanol or water would give poor yields as a solvent, since I've seen multiple references where they use exactly those as solvents for this reaction (or methanol, or THF). The only hint I could find was a suggestion that using acetic acid may be necessary when deprotecting a Cbz group from an amine, since protonating the nitrogen facilitates the reaction. A couple of references said that an aliphatic amine could poison the catalyst and require the addition of dilute acid to protonate the amine...I'm lost on why or how the poisoning occurs.
A nudge in the right direction would be greatly appreciated.
