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.2019 Oct 4;9(10):9158-9163.
doi: 10.1021/acscatal.9b03695. Epub 2019 Sep 11.

Inversion of Enantioselectivity in Allene Gas versus Allyl Acetate Reductive Aldehyde Allylation Guided by Metal-Centered Stereogenicity: An Experimental and Computational Study

Affiliations

Inversion of Enantioselectivity in Allene Gas versus Allyl Acetate Reductive Aldehyde Allylation Guided by Metal-Centered Stereogenicity: An Experimental and Computational Study

Seung Wook Kim et al. ACS Catal..

Abstract

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 vs 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)vs allyl acetate ionization (from a square planar iridium species).

Keywords: allylation; enantioselective; iridium; reductive coupling; transfer hydrogenation.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Allene feedstocks formed in petroleum cracking.
Figure 2.
Figure 2.
Milestones in metal-catalyzed allene-carbonyl reductive coupling andrelated hydrogen auto-transfer processes.
Figure 3.
Figure 3.
Diastereomeric composition of the (S)-Ir-Vand calculated thermodynamic stabilities.
Figure 4.
Figure 4.
Hypothesis for enantiodivergence in aldehyde allylations mediated bygaseous allenevs allyl acetate.
Figure 5.
Figure 5.
Computed energy profiles of the kinetic pathways leading todiastereomersD andC and, therefrom,(S)-and (R)-product enantiomers,respectively.
Figure 6.
Figure 6.
Enantioselectivity-determining aldehyde allylation transition stateswith π-allyliridium complexesD andC.Activation free energies are with respect toD andC,respectively. The (S)-tol-BINAP ligands are omitted forclarity
See this image and copyright information in PMC

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