Photorelease via photoenol lactonization is known to be slow released due to the minimized lifetimes of photoenols. Our newly designed photoremovable protecting group 1  releases alcohols in high quantum yields. Efficient photorelease of alcohol is observed in argon and oxygen saturated solutions. Photorelease mechanism is elucidated using product studies, transient spectroscopy and molecular modeling. Irradiation of 1  facilitates the intramolecular hydrogen abstraction to form biradical 2  . Biradical 2   undergoes expulsion of nitrogen molecule to form imine biradical 3  irreversibly, which undergoes intersystem crossing and hydrogen transfer to form 4  and release the alcohol moiety. In competition with biradical 2   forming imine biradical 4  , it also undergoes intersystem crossing to form photoenols Z-5   and E-5  . The efficient photorelease occurs due to the fact the imine radical 3  cannot regenerate the starting material as photoenols Z-5   & E-5  .

Novel photoremovable protecting group to achieve efficient release of alcohol via photoenol lactonization

246th National Meeting (2013)

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