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Synfacts 2019; 15(12): 1399
DOI: 10.1055/s-0039-1691256
DOI: 10.1055/s-0039-1691256
Metals in Synthesis
Asymmetric Addition of Allenes to Aldehydes
Kim SW,
Meyer CC,
Mai BK.
Liu P.
*
Krische MJ.
* University of Texas at Austin and University of Pittsburgh, USA
Inversion of Enantioselectivity in Allene Gas versus Allyl Acetate Reductive Aldehyde Allylation Guided by Metal-Centered Stereogenicity: An Experimental and Computational Study.
ACS Catal. 2019;
9: 9158-9163
Inversion of Enantioselectivity in Allene Gas versus Allyl Acetate Reductive Aldehyde Allylation Guided by Metal-Centered Stereogenicity: An Experimental and Computational Study.
ACS Catal. 2019;
9: 9158-9163
Further Information
Publication History
Publication Date:
18 November 2019 (online)
Significance
The authors report an enantioselective iridium-catalyzed allylation of aldehydes leading to chiral secondary alcohols in high yields. Interestingly, when allene instead of allyl acetate is used as a nucleophile, an inversion of enantioselectivity is observed.
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Comment
Remarkably, the authors performed an extensive experimental and computational study to rationalize the observed selectivity. Their results indicate that diastereomeric π-allyliridium-C,O-benzoate complexes, which are formed via allene hydrometalation or allyl acetate ionization, are involved.
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