The novel reactivity of O-silylthionoesters with amine nucleophiles to generate oxoamides (rather than thioamides) is described. A straightforward first-generation trimethylsilylation protocol using bistrimethylsilylacetamide (BSA) combined with the unique reactivity of the O-silylthionoesters toward 1° and 2° amines to generate oxoamides provides the simplest means of activating a thiol acid for peptide bond formation at neutral pH. Excellent stereoretention is observed.
The novel reactivity of O-silylthionoesters with n class="Chemical">amine nucleophiles to generate oxoamides (rather than thioamides) is described. A straightforward first-generation trimethylsilylation protocol using bistrimethylsilylacetamide (BSA) combined with the unique reactivity of the O-silylthionoesters toward 1° and 2° amines to generate oxoamidesprovides the simplest means of activating a thiol acid for peptide bond formation at neutral pH. Excellent stereoretention is observed.
Authors: Andrew G Roberts; Eric V Johnston; Jae-Hung Shieh; Joseph P Sondey; Ronald C Hendrickson; Malcolm A S Moore; Samuel J Danishefsky Journal: J Am Chem Soc Date: 2015-10-01 Impact factor: 15.419