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. 2016 Jul 6;138(26):8084-7.
doi: 10.1021/jacs.6b04818. Epub 2016 Jun 22.

Silyl Radical Activation of Alkyl Halides in Metallaphotoredox Catalysis: A Unique Pathway for Cross-Electrophile Coupling

Patricia Zhang  1 , Chi Chip Le  1 , David W C MacMillan  1
Affiliations

Silyl Radical Activation of Alkyl Halides in Metallaphotoredox Catalysis: A Unique Pathway for Cross-Electrophile Coupling

Patricia Zhang et al. J Am Chem Soc. .

Abstract

A strategy for cross-electrophile coupling has been developed via the merger of photoredox and transition metal catalysis. In this report, we demonstrate the use of commercially available tris(trimethylsilyl)silane with metallaphotoredox catalysis to efficiently couple alkyl bromides with aryl or heteroaryl bromides in excellent yields. We hypothesize that a photocatalytically generated silyl radical species can perform halogen-atom abstraction to activate alkyl halides as nucleophilic cross-coupling partners. This protocol allows the use of mild yet robust conditions to construct Csp(3)-Csp(2) bonds generically via a unique cross-coupling pathway.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Alkyl bromide–aryl bromide coupling via photoredox.
Figure 2
Figure 2
Mechanistic cycle for silyl-mediated cross-coupling.
See this image and copyright information in PMC

References

    1. de Meijere A, Diederich F, editors. Metal-Catalyzed Cross-Coupling Reactions. 2. Wiley-VCH; Weinheim, Germany: 2004.
    2. Jana R, Pathak TP, Sigman MS. Chem Rev. 2011;111:1417. - PMC - PubMed

    1. For some reviews of the use of nickel in cross-coupling methods, see: Tasker SZ, Standley EA, Jamison TF. Nature. 2014;509:299.Netherton MR, Fu GC. Adv Synth Catal. 2004;346:1525.Rudolph A, Lautens M. Angew Chem, Int Ed. 2009;48:2656.

    1. Knappke CEI, Grupe S, Gärtner D, Corpet M, Gosmini C, Jacobi von Wangelin A. Chem - Eur J. 2014;20:6828. - PubMed
    1. Czaplik WM, Mayer M, Jacobi von Wangelin A. Synlett. 2009;2009:2931. - PubMed
    2. Krasovskiy A, Duplais C, Lipshutz BH. J Am Chem Soc. 2009;131:15592. - PMC - PubMed
    3. Amatore M, Gosmini C. Chem - Eur J. 2010;16:5848. - PubMed
    4. Durandetti M, Gosmini C, Périchon J. Tetrahedron. 2007;63:1146.
    1. Everson DA, Jones BA, Weix DJ. J Am Chem Soc. 2012;134:6146. - PMC - PubMed
    2. Wang S, Qian Q, Gong H. Org Lett. 2012;14:3352. - PubMed
    3. Molander GA, Traister KM, O’Neill BT. J Org Chem. 2014;79:5771. - PubMed
    4. Bhonde VR, O’Neill BT, Buchwald SL. Angew Chem, Int Ed. 2016;55:1849. - PubMed

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