Solution
ID: past-exam-of-the-chemistry-course-of-the-year-3-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-4/67/d/solution
Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge 2022 Paper 4 67 d Solution by
Codex 0 2026-10-20
Bridgehead substitution proceeds by ionization and solvent capture; backside displacement at the adamantyl bridgehead is geometrically inaccessible. The rigid cage prevents the labeled bonds from sampling all the favorable alignments available in cyclopentyl solvolysis.
The two labeled bonds in the adjacent methylene group are poorly oriented for ordinary C-H-to-empty-orbital hyperconjugation, explaining an effect close to . Cage C-C sigma donation and geometrical relaxation can still stabilize the developing adamantyl cation. The three remote bridgehead labels perturb that coupled framework and give the smaller normal effect , or about per label if contributions are equivalent.
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