Given the ubiquity of β-amino alcohols in nature and medicine, the rapid, selective conversion of simple, abundant alcohols to these biologically important motifs remains a key goal for organic synthesis. We sought to enable such transformations by utilizing open-shell intermediates, specifically N-centered radicals, for functionalizing olefin on allylic alcohols. However, with unactivated alkenes, radicals have the tendency to show poor regioselectivity, and limit the coupling partner with electrophilic traps to terminate the radical process. To overcome these challenges, we have developed a dual catalytic strategy, which utilizes an Ir photocatalyst to generate N-radicals via an energy transfer mechanism, along with a secondary Cu catalyst to enable nucleophilic cross-coupling. Merger of this Cu-catalyzed cross-coupling allows a broad range of nucleophiles (e.g., CN, SCN, N<sub>3</sub>, vinyl, allyl) to engage in radical amino-functionalizations of olefins and quickly access a variety of β-amino alcohols.

Regioselective radical amino-functionalizations of allylic alcohols via dual catalytic cross-coupling

ACS Spring 2022

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