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

Chen, Wenyong; Chen, Ming; Hartwig, John F.

doi:10.1021/ja506500u

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

Abstract

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.

Authors:

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

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

Publication Date:: Thu Oct 30 00:00:00 EDT 2014

Research Org.:: Univ. of California, Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1163792

Alternate Identifier(s):: OSTI ID: 1345809

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Journal Article: Published Article

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Name: Journal of the American Chemical Society Journal Volume: 136 Journal Issue: 45; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Chen, Wenyong, Chen, Ming, and Hartwig, John F. Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates.  United States: N. p., 2014. 
        Web.  doi:10.1021/ja506500u.

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                    Chen, Wenyong, Chen, Ming, & Hartwig, John F. Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates.  United States.  https://doi.org/10.1021/ja506500u

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                    Chen, Wenyong, Chen, Ming, and Hartwig, John F. 2014.  
        "Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates".  United States.  https://doi.org/10.1021/ja506500u.

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@article{osti_1163792,

  title        = {Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates},

  author       = {Chen, Wenyong and Chen, Ming and Hartwig, John F.},

  abstractNote = {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.},

  doi          = {10.1021/ja506500u},

  url          = {https://www.osti.gov/biblio/1163792},
  journal      = {Journal of the American Chemical Society},

  issn         = {0002-7863},

  number       = 45,

  volume       = 136,

  place        = {United States},

  year         = {Thu Oct 30 00:00:00 EDT 2014},

  month        = {Thu Oct 30 00:00:00 EDT 2014}

}

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Cited by: 64 works

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Scheme 1: Pd- and Ir-Catalyzed Allylation of Ketones

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