Open AccessInversion 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 , chemistry , enantioselective synthesis , aldehyde , medicinal chemistry , organic chemistry , catalysis
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).