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. 2009;48(51):9705-8.
doi: 10.1002/anie.200904474.

Strain release in C-H bond activation?

Ke Chen  1 , Albert Eschenmoser, Phil S Baran
Affiliations

Strain release in C-H bond activation?

Ke Chen et al. Angew Chem Int Ed Engl. 2009.

Abstract

What a relief! In 1955 the principle of strain release was put forward to explain the differing reactivity of axial and equitorial alcohols during oxidation. Our findings suggest that this same rationale may account for the differing rates of activation between axial and equitorial C–H bonds in C–H activation processes. In conjunction with steric and electronic considerations, strain-release can be used to qualitatively predict relative rates and site specificity of C–H activation in complex settings.

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Figures

Figure 1
Figure 1
Observations from the literature.
Figure 2
Figure 2
(A) The principle of strain-release during alcohol oxidation; (B) Site-selective C–H oxidation: A strain-release phenomena?
Figure 3
Figure 3
The design of an eudesmane-based probe to account for the enhanced reactivity of equatorial C-H's.
Scheme 1
Scheme 1
Synthesis of eudesmane 3.
Scheme 2
Scheme 2
TFDO- and Ozone-mediated oxidation of a 1:1 mixture of 1 and 3 clearly reveals the strain-release phenomenon in tertiary C–H oxidation.
Scheme 3
Scheme 3
Strain-release is a minor factor in methylene C-H activation.
Scheme 4
Scheme 4
Strain-release may be an important contributor in methylene activation in complex settings.
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