The use of gaseous allene as an allyl pronucleophile in enantioselective aldehyde reductive coupling is described. Notably, using the same antipode of chiral ligand, ( S )-tol-BINAP, an inversion of enantioselectivity is observed for allene versus allyl acetate pronucleophiles. Experimental and computational studies corroborate intervention of diastereomeric π-allyliridium- C,O -benzoate complexes, which arise via allene hydrometalation (from a pentacoordinate iridium hydride) versus allyl acetate ionization (from a square planar iridium species).
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Kim et al. (2019) studied this question.
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