Abstract
A series of dipeptides 1 was synthesized that at the N-site contained 3-(N-phthalimidoadamantane-1-carboxylic acid and at the C-site different aliphatic or aromatic l- or d-amino acids. The photochemical reaction of dipeptides 1 under acetone-sensitized conditions gave simple decarboxylation products 6, and decarboxylation-induced cyclization products 7, as well as some secondary products 8 and 9 formed by elimination of H2O or ring enlargement, respectively. Molecules 9 undergo secondary photoinduced H-abstractions by the phthalimide chromophore, delivering more complex polycycles 11. The photodecarboxylation-induced cyclization to 7 was observed only with phenylalanine (Phe), proline (Pro), leucine (Leu) and isoleucine (Ile). Contrary to dipeptides with Phe, the cyclization takes place with almost complete racemization at the amino acid chiral center, but diastereoselectively giving only one pair of enantiomers. The conducted investigation is important as it provides the breath and the scope of dipeptide cyclizations activated by phthalimides.
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This research was funded by the Croatian Science Foundation (HRZZ grants no. HRZZ IP-2014-09-6312 and HRZZ-IP-2019-04-8008).
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Supplementary file1 (PDF 11597 KB) Synthetic procedures and selected photochemical experiments, HPLC chromatograms on chiral stationary phases, computational data and copies of 1H and 13C NMR spectra.
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Sohora, M., Sović, I., Spahić, Z. et al. Photochemistry of phthalimidoadamantane dipeptides: effect of amino acid side chain on photocyclization. Photochem Photobiol Sci 22, 2071–2080 (2023). https://doi.org/10.1007/s43630-023-00430-4
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DOI: https://doi.org/10.1007/s43630-023-00430-4