Strain Release in CH Bond Activation?

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We use the term “CH bond nucleophilicity” when referring to the “electronic reactivity factor”. It seems to us that this term pragmatically denotes the effect of what hyperconjugative and inductive electronic effects might transmit from neighboring substituents to the reaction site. Thus this term can refer to both activation as well as deactivation of the CH bond by neighboring substituents towards electrophilic “CH activation” insertion reactions.

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The chemical shift of the reaction center in probe3is exactly 0.1 ppm higher than in1 which might indicate somewhat less CH bond nucleophilicity. However such a small difference should be regarded as negligible. For example the13C shift of the tertiary carbons incisandtransdecalin differ by ca. 7 ppm yet the rate ratio of oxidation with ozone is only ca. 5.6:1 (see Scheme 1 and ref. [4a]). See ref. [11b] for a correlation of13C NMR shift and fractional charge.

10.1021/jo00902a035