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.
|Original language||English (US)|
|Number of pages||6|
|Journal||Angewandte Chemie - International Edition|
|State||Published - Sep 6 2021|
All Science Journal Classification (ASJC) codes
- C−C cleavage
- alkoxy radicals