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.
Nielsen
Thomas E
TE
SPOCC Centre, Carlsberg Laboratory, Gamle Carlsberg Vej 10, DK-2500 Valby, Denmark.
Meldal
Morten
M
D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D020650:Combinatorial Chemistry Techniques; D005998:Glycine / Q000031:analogs & derivatives / Q000737:chemistry; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis*; D007546:Isoquinolines / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D009993:Osmium Tetroxide / Q000737:chemistry; D010084:Oxidation-Reduction; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry; D012974:Sodium Iodide / Q000737:chemistry
D000447:Aldehydes; D000475:Alkenes; D006575:Heterocyclic Compounds, 3-Ring; D007546:Isoquinolines; D011758:Pyrroles; D012974:Sodium Iodide; D009993:Osmium Tetroxide; D005998:Glycine