Problem 3d, Chapter 4

degenerate 3,3-shift for 1,4-dimethylenecycloheptane, with deuterium markers

In this reaction, we see a degenerate [3,3] shift from a boat conformation of the cycloheptane ring. The boat structure and the transition state for the reaction are shown below, with their energies.

Energies calculated at the HF/6-31G* level with ZPE correction.

boat structure

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transition state structure

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The transition state is 61 kcal/mol above the boat conformation, which is itself about 3 kcal/mol above the chair conformation. However, the reaction cannot take place from the chair conformation of the cycloheptane ring.

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