Photoinduced nickel-catalysed enantioconvergent sp3–sp3 coupling of unactivated olefins and aziridines

Abstract

Catalytic sp³–sp³ bond-forming reactions have been the subject of considerable interest in both academic and pharmaceutical laboratories. This is largely due to the observation that a higher content of sp³-hybridized carbons has recently been shown to improve several molecular attributes that contribute to clinical success. Although the ready availability of unactivated olefins and aziridines makes them ideal precursors to forge enantioenriched sp³–sp³ architectures with added-value amine functions, an enantioconvergent catalytic scenario of these counterparts has not yet been realized. Here we describe a nickel-catalysed blueprint that enables the enantioselective construction of amine-containing sp³–sp³ architectures via photoinduced enantioconvergent coupling of racemic aziridines with alkylzirconium reagents generated in situ from unactivated terminal and even internal olefins. The broad applicability of this protocol is illustrated in a series of late-stage diversification of advanced synthetic intermediates.