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Abstract
Whereas considerable advances have recently been achieved in radical-involved
catalytic asymmetric C-N bond formation, there has been little progress in the corresponding
C-O bond-forming processes. Here we describe a photoinduced copper-catalyzed
cross-coupling of readily oxime esters and 1,3-dienes to generate diversely
substituted allylic esters with high regio- and enantioselectivity (>75
examples; up to 95% ee). The reaction proceeds at room temperature under
excitation by purple light-emitting diodes and features the use of a single, earth-abundant
copper-based chiral catalyst as both the photoredox catalyst for radical
generation and the source of asymmetric induction in C-O coupling. Combined experimental
and DFT computational studies suggest the formation of π-allylcopper complex from redox-active oxime esters as bifunctional
reagents and 1,3-dienes through a radical-polar crossover process.
Supplementary materials
Title
Supporting Information-20210507
Description
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