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. 2017 May 5;19(9):2426-2429.
doi: 10.1021/acs.orglett.7b00989. Epub 2017 Apr 26.

Synergistic Visible-Light Photoredox/Nickel-Catalyzed Synthesis of Aliphatic Ketones via N-C Cleavage of Imides

Javad Amani  1 , Rauful Alam  1 , Shorouk Badir  1 , Gary A Molander  1
Affiliations

Synergistic Visible-Light Photoredox/Nickel-Catalyzed Synthesis of Aliphatic Ketones via N-C Cleavage of Imides

Javad Amani et al. Org Lett. .

Abstract

An electrophilic, imide-based, visible-light-promoted photoredox/Ni-catalyzed cross-coupling reaction for the synthesis of aliphatic ketones has been developed. This protocol proceeds through N-C(O) bond activation, made possible through the lower activation energy for metal insertion into this bond due to delocalization of the lone pair of electrons on the nitrogen by electron-withdrawing groups. The operationally simple and mild cross-coupling reaction is performed at ambient temperature and exhibits tolerance for a variety of functional groups.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Photoredox/Ni Dual-Catalytic Cross-Coupling of Amides with 2° Alkyl R–BF3K
Scheme 2
Scheme 2. Graphical Chart of P/IS of the Cross-Coupling of a Variety of Activated Amides with Cyclohexyltrifluoroborate
Scheme 3
Scheme 3. Proposed Mechanism for the Photoredox Cross-Coupling of N-Acylpyrrolidine-2,5-diones with Alkyl–BF3K
Scheme 4
Scheme 4. Scope of the Cross-Coupling Reaction of N-Acyl Succinimides with Potassium Alkyltrifluoroborates
Reaction performed on a 4.5 mmol scale with 1.5 mol % Ir photocatalyst 1 and 3 mol % [Ni(dtbbpy)(H2O)4]Cl2.
See this image and copyright information in PMC

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References

    1. Gooßen L. J.; Rodriguez N.; Gooßen K. Angew. Chem., Int. Ed. 2008, 47, 3100.10.1002/anie.200704782. - DOI - PubMed
    2. Dieter R. K. Tetrahedron 1999, 55, 4177.10.1016/S0040-4020(99)00184-2. - DOI
    1. Blangetti M.; Rosso H.; Prandi C.; Deagostino A.; Venturello P. Molecules 2013, 18, 1188.10.3390/molecules18011188. - DOI - PMC - PubMed
    2. Urawa Y.; Ogura K. Tetrahedron Lett. 2003, 44, 271.10.1016/S0040-4039(02)02501-7. - DOI
    3. Haddach M.; McCarthy J. R. Tetrahedron Lett. 1999, 40, 3109.10.1016/S0040-4039(99)00476-1. - DOI
    4. Bumagin N. A.; Korolev D. N. Tetrahedron Lett. 1999, 40, 3057.10.1016/S0040-4039(99)00364-0. - DOI
    1. Gooßen L. J.; Ghosh K. Angew. Chem., Int. Ed. 2001, 40, 3458.10.1002/1521-3773(20010917)40:18<3458::AID-ANIE3458>3.0.CO;2-0. - DOI - PubMed
    2. Kakino R.; Yasumi S.; Shimizu I.; Yamamoto A. Bull. Chem. Soc. Jpn. 2002, 75, 137.10.1246/bcsj.75.137. - DOI
    3. Kakino R.; Shimizu I.; Yamamoto A. Bull. Chem. Soc. Jpn. 2001, 74, 371.10.1246/bcsj.74.371. - DOI
    1. Tatamidani H.; Kakiuchi F.; Chatani N. Org. Lett. 2004, 6, 3597.10.1021/ol048513o. - DOI - PubMed
    2. Tatamidani H.; Yokota K.; Kakiuchi F.; Chatani N. J. Org. Chem. 2004, 69, 5615.10.1021/jo0492719. - DOI - PubMed
    1. Liebeskind L. S.; Srogl J. J. Am. Chem. Soc. 2000, 122, 11260.10.1021/ja005613q. - DOI
    2. Prokopcova H.; Kappe C. O. Angew. Chem., Int. Ed. 2009, 48, 2276.10.1002/anie.200802842. - DOI - PubMed

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