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CuH-catalyzed reductive coupling processes involving carbonyl compounds and
imines has become an attractive alternative to traditional methods for
stereoselective addition to carbonyls due to the ability to use readily
accessible and stable olefin-derived pronucleophiles as surrogates for
organometallic reagents. However, the inability to use aldehydes, which traditionally
reduce too rapidly in the presence of copper hydride complexes to be viable
substrates, has been a major limitation. We show that by exploiting relative
concentration effects through slow addition, we can invert this intrinsic
reactivity and achieve the reductive coupling of 1,3-dienes with aldehydes.
Using this method, both aromatic and aliphatic aldehydes can be transformed to
valuable products with high levels of diastereo- and enantioselectivity and in
the presence of many useful functional groups. Furthermore, using a combination
of theoretical (DFT) and experimental methods, important mechanistic features
of this reaction related to stereo- and chemoselectivity were uncovered.