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Review
. 2011 Apr 4;50(15):3362-74.
doi: 10.1002/anie.201006368. Epub 2011 Mar 16.

If C-H bonds could talk: selective C-H bond oxidation

Timothy Newhouse  1 , Phil S Baran
Affiliations
Review

If C-H bonds could talk: selective C-H bond oxidation

Timothy Newhouse et al. Angew Chem Int Ed Engl. .

Abstract

C-H oxidation has a long history and an ongoing presence in research at the forefront of chemistry and interrelated fields. As such, numerous highly useful articles and reviews have been written on this subject. Logically, these are generally written from the perspective of the scope and limitations of the reagents employed. This Minireview instead attempts to emphasize chemoselectivity imposed by the nature of the substrate. Consequently, many landmark discoveries in the field of C-H oxidation are not discussed, but hopefully the perspective taken herein will allow C-H oxidation reactions to be more readily incorporated into synthetic planning.

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Figures

Figure 1
Figure 1
Electron-Withdrawing groups influence the site of C–H activation.
Figure 2
Figure 2
Hyperconjugation by cyclopropanes activates neighboring C–H bonds
Figure 3
Figure 3
Hyperconjugation by heteroatoms activates neighboring C–H bonds.
Figure 4
Figure 4
Oxidation of allylic and benzylic systems.
Figure 5
Figure 5
Steric hindrance effects the rate of C–H oxidation.
Figure 6
Figure 6
Strain release may be an important factor in controling site-selectivity in C–H activation reactions.
Figure 7
Figure 7
Directed oxidations offer an opportunity to effect positional selectivity.
Figure 8
Figure 8
A number of directing groups may be employed in C–H activation.
Figure 9
Figure 9
C–H activation of sp2 centers presents unique challenges.
Figure 10
Figure 10
Unique geometries of bicyclic systems results in varied selectivity.
Figure 11
Figure 11
Additional examples of C–H oxidation.
See this image and copyright information in PMC

References

    1. For representative examples and the importance of C–H activation in chemical synthesis, see: Gaich T, Baran PS. J. Org. Chem. 2010;75:4657–4673.

    1. Newhouse T, Baran PS, Hoffmann RW. Chem. Soc. Rev. 2009;39:3010–3021. - PMC - PubMed

    1. For an overview with respect to taxol, see: Ishihara Y, Baran PS. Synlett. 2010;12:1733–1745.

    1. For reviews on C–H oxidation, see: Barton DHR, Doller D. Acc. Chem. Res. 1992;25:504–512. Barton DHR. Tetrahedron. 1998;54:5805–5817. Doyle MP, Forbes DC. Chem. Rev. 1998;98:911–935. Müller P, Fruit C. Chem. Rev. 2003;103:2905–2919. Davies HML, Beckwith REJ. Chem. Rev. 2003;103:2861–2904. Punniyamurthy T, Velusamy S, Iqbal J. Chem. Rev. 2005;105:2329–2363. Godula K, Sames D. Science. 2006;312:67–72. Dick AR, Sanford MS. Tetrahedron. 2006;62:2439–2463. Davies HML, Manning JR. Nature. 2008;451:417–424. Giri R, Shi B-F, Engle KM, Maugel N, Yu J-Q. Chem. Soc. Rev. 2009;38:3242–3271. Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010;110:704–724.

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