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

Seung Wook Kim | Zendy; Cole C. Meyer | Zendy; Binh Khanh | Zendy; Peng Liu | Zendy; Michael J. Krische | Zendy

Open Access

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

Author(s) -

Seung Wook Kim,

Cole C. Meyer,

Binh Khanh,

Peng Liu,

Michael J. Krische

Publication year - 2019

Publication title -

acs catalysis

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 4.898

H-Index - 198

ISSN - 2155-5435

DOI - 10.1021/acscatal.9b03695

Subject(s) - allene , aldehyde , inversion (geology) , chemistry , metal , catalysis , combinatorial chemistry , computational chemistry , organic chemistry , paleontology , structural basin , biology

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).

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