Solution

ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-3/44/b/iv/solution

The Woodward-Hoffmann rules for a electron electrocyclic reaction permit thermal disrotation and photochemical conrotation. Here six electrons mean . For the ground-state six-electron chain, opposite terminal rotations match the terminal phases of its highest occupied orbital as the closing sigma bond forms. A one-electron excitation changes the relevant occupancy and reverses the allowed rotational mode. Thus A opens conrotatorily under light to the specified B, while B closes disrotatorily on heating. Reversing the rotational mode changes the adjacent methyl relationship from cis to trans, exactly as in C.

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