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1,3‐Alkyl Transposition in Allylic Alcohols Enabled by Proton‐Coupled Electron Transfer
Author(s) -
Zhao Kuo,
Seidler Gesa,
Knowles Robert R.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202105285
Subject(s) - allylic rearrangement , chemistry , alkyl , ketone , isomerization , alkoxy group , photochemistry , bond cleavage , electron transfer , medicinal chemistry , organic chemistry , catalysis
A method is described for the isomerization of acyclic allylic alcohols into β‐functionalized ketones via 1,3‐alkyl transposition. This reaction proceeds via light‐driven proton‐coupled electron transfer (PCET) activation of the O−H bond in the allylic alcohol substrate, followed by C−C β‐scission of the resulting alkoxy radical. The transient alkyl radical and enone acceptor generated in the scission event subsequently recombine via radical conjugate addition to deliver β‐functionalized ketone products. A variety of allylic alcohol substrates bearing alkyl and acyl migratory groups were successfully accommodated. Insights from mechanistic studies led to a modified reaction protocol that improves reaction performance for challenging substrates.