Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates

Journal Article · Thu Oct 30 00:00:00 EDT 2014 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja506500u· OSTI ID:1163792

Chen, Wenyong ^[1]; Chen, Ming ^[1]; Hartwig, John F. ^[1]

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1. Department of Chemistry, University of California, Berkeley, California 94720, United States

Here, we report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

• Research Organization: Univ. of California, Berkeley, CA (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• Grant/Contract Number: AC02-05CH11231
• OSTI ID: 1163792
• Alternate ID(s): OSTI ID: 1345809
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 136 Journal Issue: 45; ISSN 0002-7863
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY