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. 2014 Jul 1;1(5):567-581.
doi: 10.1039/c4qo00053f. Epub 2014 Mar 27.

Direct activation of relatively unstrained carbon-carbon bonds in homogeneous systems

Alpay Dermenci  1 , Jotham W Coe  1 , Guangbin Dong  2
Affiliations

Direct activation of relatively unstrained carbon-carbon bonds in homogeneous systems

Alpay Dermenci et al. Org Chem Front. .

Abstract

New modes of chemical reactivity are of high value to synthetic organic chemistry. In this vein, carbon-carbon (C-C) activation is an emerging field that offers new possibilities for synthesizing valuable complex molecules. This review discusses the pioneering stoichiometric discoveries in this field up to the most recent synthetic applications that apply catalytic transformations. Specifically, the review focuses on C-C activation in relatively unstrained systems, including stoichiometric reactions, chelation-directed and chelation-free catalytic reactions. While the field of C-C activation of relatively unstrained systems is underdeveloped, we expect that this review will provide insight into new developments and pave the path for robust, practical applications.

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Figures

Scheme 1
Scheme 1
Rh-promoted C–C activation of a chiral quinoline derived substrate.
Scheme 2
Scheme 2
Ru-promoted C–C activation of hexafluoroketone.
Scheme 3
Scheme 3
Zr- and Ti-mediated C–C activation of diynes.
Scheme 4
Scheme 4
Activation of strong C–C bonds in pincer ligands reported by Milstein and co-workers.
Scheme 5
Scheme 5
Decarbonylation of chalcone by unique Rh complex 36.
Scheme 6
Scheme 6
Demethylation of acetone via C-C activation.
Scheme 7
Scheme 7
Phosphonite-directed C–C activation and carbonylation with Ni.
Scheme 8
Scheme 8
C–C activation and decarbonylation of benzophenone with Ni as the metal center.
Scheme 9
Scheme 9
Proposed catalytic cycle for C–C activation of PCP ligand.
Scheme 10
Scheme 10
Proposed mechanism for oxazoline-directed C–C activation.
Scheme 11
Scheme 11
Mechanism of alkyl-exchange via C–C bond activation.
Scheme 12
Scheme 12
Proposed mechanism for Rh-catalyzed ring-opening of cycloalkanoketimines.
Scheme 13
Scheme 13
Rh-catalyzed skeletal rearrangement of bicycle[3.2.1]octan-2-one.
Scheme 14
Scheme 14
Mechanism for the synthesis of all carbon quaternary centers.
Scheme 15
Scheme 15
Proposed catalytic cycle for the C–C activation and decar-bonylation of biaryl ketones.
Scheme 16
Scheme 16
Utilization of the Rh-catalyzed decarbonylation to synthesize highly conjugated rod-like structures.
Scheme 17
Scheme 17
Proposed mechanism for the Rh-catalyzed decarbonylation of diynones.
Scheme 18
Scheme 18
The proposed mechanism for Rh-catalyzed cleavage of PCP.
See this image and copyright information in PMC

References

    1. Nakao Y. Catalytic C–CN Bond Activation. In: Dong G, editor. C–C Activation; Topics in Current Chemistry. Springer-Verlag; Berlin, Heidelberg: 2014. in press. - PubMed
    2. Moebius DC, Rendina VL, Kingsbury JS. Catalysis of Diazoalkane–Carbonyl Homologation How New Developments in Hydrazone Oxidation Enable the Carbon Insertion Strategy for Synthesis. In: Dong G, editor. C–C Activation; Topics in Current Chemistry. Springer-Verlag; Berlin, Heidelberg: 2014. in press. - PubMed
    1. Rodríguez N, Gooßen LJ. Chem Soc Rev. 2011;40:5030–5048. - PubMed

    1. For key references, see: Necas D, Kotora M. Org Lett. 2008;10:5261–5263.Necas D, Tursky M, Kotora M. J Am Chem Soc. 2004;126:10222–10223. and references therein.

    1. For a lead reference, see: Kuzmanich G, Natarajan A, Shi Y, Patrick BO, Scheffer JR, Garcia-Garibay MA. Photochem Photobiol Sci. 2011;10:1731–1734. and references therein.

    1. For reviews on C–C activation, see: Rybtchinski B, Milstein D. Angew Chem, Int Ed. 1999;38:870–883.Jun CH, Lee JH. Pure Appl Chem. 2004;76:577–587.Jun CH. Chem Soc Rev. 2004;33:610–618.Kondo T, Mitsudo Ta. Chem Lett. 2005;34:1462–1467.Kondo T. Synlett. 2008:629–644.Ruhland K. Eur J Org Chem. 2012:2683–2706.Klein JEMN, Pliekter B. Org Biomol Chem. 2013;11:1271–1279.Necas D, Kotora M. Curr Org Chem. 2007;11:1566–1591.Korotvicka A, Necas D, Kotora M. Curr Org Chem. 2012;16:1170–1214.

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