Highly efficient solid-phase oxidative cleavage of olefins by OsO4-NalO4 in the intramolecular N-acyliminium Pictet-Spengler reaction

[reaction: see text] In the present investigation, solid-supported peptide olefins were converted quantitatively to aldehydes via the OsO(4)-NaIO(4)-mediated oxidative cleavage reaction. Addition of DABCO was essential to efficiently suppress the formation of hydroxymethyl ketone side products. The generated aldehydes were used in intramolecular N-acyliminium Pictet-Spengler reactions to produce highly pure pyrroloisoquinoline derivatives. The methodology was extended to allylglycine derivatives to enable the incorporation of pyrroloisoquinoline scaffolds within peptides.