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. 2013 Dec 11;135(49):18323-6.
doi: 10.1021/ja410478a. Epub 2013 Nov 22.

Direct β-functionalization of cyclic ketones with aryl ketones via the merger of photoredox and organocatalysis

Filip R Petronijević  1 , Manuel Nappi, David W C MacMillan
Affiliations

Direct β-functionalization of cyclic ketones with aryl ketones via the merger of photoredox and organocatalysis

Filip R Petronijević et al. J Am Chem Soc. .

Abstract

The direct β-coupling of cyclic ketones with aryl ketones has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Diaryl oxymethyl or aryl-alkyl oxymethyl radicals, transiently generated via single-electron reduction of ketone precursors, readily merge with β-enaminyl radical species, generated by photon-induced enamine oxidation, to produce γ-hydroxyketone adducts. Experimental evidence indicates that two discrete reaction pathways can be operable in this process depending upon the nature of the ketyl radical precursor and the photocatalyst.

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Figures

Figure 1
Figure 1
Ir(ppy)3 Emission Quenching with Benzophenone and Enamine 4.
Figure 2
Figure 2
Ir(p-MeO-ppy)3 Emission Quenching with Acetophenone and Enamine 4.
Scheme 1
Scheme 1
Proposed Mechanism for the β-Ketone Coupling.
See this image and copyright information in PMC

References

    1. Pirnot MT, Rankic DA, Martin DBC, MacMillan DWC. Science. 2013;339:1593. - PMC - PubMed
    2. Zhang S-L, Xie H-X, Zhu J, Li H, Zhang X-S, Li J, Wang W. Nat. Commun. 2011;2:211. - PubMed
    3. Leskinen MV, Yip K-T, Valkonen A, Pihko PM. J. Am. Chem. Soc. 2012;134:5750. - PubMed
    1. Carey FA, Sundberg RJ. Advanced Organic Chemistry: Part B: Reactions and Synthesis. New York: Springer; 2001.
    1. Mukherjee S, Yang JW, Hoffmann S, List B. Chem. Rev. 2007;107:5471. - PubMed
    2. Evans DA, Helmchen G, Rüping M. Asymmetric Synthesis–The Essentials. Wiley-VCH: Weinheim; 2006.

    1. For direct β-functionalizations of amides, esters, or oximes, see: Zaitsev VG, Shabashov D, Daugulis O. J. Am. Chem. Soc. 2005;127:13154. Wasa M, Engle KM, Yu J-Q. J. Am. Chem. Soc. 2009;131:9886. Stowers KJ, Kubota A, Sanford MS. Chem. Sci. 2012;3:3192. Renaudat A, Jean-Gérard L, Jazzar R, Kefalidis CE, Clot E, Baudoin O. Angew. Chem. Int. Ed. 2010;49:7261.

    1. Yamamoto H. Lewis Acids in Organic Synthesis. New York: Wiley-VCH; 2000.
    2. Crabtree RH. The Organometallic Chemistry of the Transition Metals. Hoboken: Wiley-Interscience; 2005.
    3. Noyori R. Asymmetric Catalysis in Organic Synthesis. New York: Wiley-Interscience; 1994.
    4. Ojima I. Catalytic Asymmetric Synthesis. New York: Wiley-VCH; 2000.
    5. Lelais G, MacMillan DWC. Aldrichim. Acta. 2006;39:79.
    6. Taylor MS, Jacobsen EN. Angew. Chem. Int. Ed. 2006;45:1520. - PubMed

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