Ultrafast Adiabatic Photodehydration of 2‐Hydroxymethylphenol and the Formation of Quinone Methide

• Published in: Chemistry : a European journal 2018-07, Vol.24 (37), p.9426-9435
• Main Authors: Škalamera, Đani, Antol, Ivana, Mlinarić‐Majerski, Kata, Vančik, Hrvoj, Phillips, David Lee, Ma, Jiani, Basarić, Nikola
• Format: Article
• Language: English
• Subjects: Adiabatic; Adiabatic flow; Chemical compounds; Chemistry; cryochemistry; Deactivation; density functional calculations; Deoxyribonucleic acid; DNA; Hydrogen bonds; Infrared spectroscopy; Intermediates; Pharmacology; Phenolic compounds; Phenols; Photochemical reactions; Photochemicals; Photochemistry; Photoexcitation; Proteins; quinone methides; Quinones; Reaction mechanisms; transient spectroscopy
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201801543

The photochemical reactivity of 2‐hydroxymethylphenol (1) was investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. In addition, theoretical studies were performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway to obtain a better understanding of the reaction mechanism. The main finding of this work is that photodehydration of 1 takes place in an ultrafast adiabatic photochemical reaction without any clear intermediate, delivering quinone methide (QM) in the excited state. Upon photoexcitation to a higher vibrational level of the singlet excited state, 1 undergoes vibrational relaxation leading to two photochemical pathways, one by which synchronous elimination of H2O gives QM 2 in its S1 state and the other by which homolytic cleavage of the phenolic O−H bond produces a phenoxyl radical (S0). Both are ultrafast processes that occur within a picosecond. The excited state of QM 2 (S1) probably deactivates to S0 through a conical intersection to give QM 2 (S0), which subsequently delivers benzoxete 4. Elucidation of the reaction mechanisms for the photodehydration of phenols by which QMs are formed is important to tune the reactivity of QMs with DNA and proteins for the potential application of QMs in medicine as therapeutic agents. Dry run: The photochemical reactivity of 2‐hydroxymethylphenol is investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. Theoretical studies are also performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway.