Husak, Antonija; Noichl, Benjamin; Šumanovac Ramljak, Tatjana; Sohora, Margareta; Škalamera, Đani; Budiša, Nedeljko; Basarić, Nikola
(2016)
Photochemical formation of quinone methides from peptides containing modified tyrosine.
Organic and Biomolecular Chemistry, 14
(46).
pp. 10894-10905.
ISSN 1477-0520
Abstract
We have demonstrated that quinone methide (QM) precursors can be introduced in the peptide structure and used as photoswithcable units for the peptide modifications. QM precursor 1 was prepared from protected tyrosine in a Mannich reaction, and further used as a building block in the peptide synthesis. Moreover, peptides containing tyrosine can be transformed to photoactivable QM precursor by a Mannich reaction which can afford monosubstituted derivatives 2 or bis-substituted derivatives 3. Photochemical reactivity of modified tyrosine 1 and dipeptides 2 and 3 was studied by preparative irradiations in CH3OH where photodeamination and photomethanolysis occur. QM precursors incorporated in peptides undergo photomethanolysis with quantum efficiency ΦR = 0.1-0.2, wherein the peptide backbone does not affect their photochemical reactivity. QMs formed from dipeptides were detected by laser flash photolysis (λmax ≈ 400 nm, τ = 100 μs- 20 ms) and their reactivity with nucleophiles was studied. Consequently, QM precursors derived from tyrosine can be a part of the peptide backbone which can be transformed into QMs upon electronic excitation, leading to the reactions of peptides with different reagents. This proof of principle showing ability to photochemically trigger peptide modifications and interactions with other molecules can have numerous applications in organic synthesis, material science, biology and medicine.
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