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/c/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 c Solution by
Codex 0 2026-10-20
The natural mechanism is ionizing solvolysis: C-OTs cleavage gives a cyclopentyl cation/ion pair, capture by acetic acid gives the protonated acetate ester, and deprotonation gives product.
The effect from H/D at the leaving-group carbon is normal alpha-secondary: that carbon develops trigonal carbocation character. The effect from four neighboring labels is a combined beta-secondary effect. Adjacent C-H sigma bonds stabilize the developing empty p orbital by hyperconjugation; replacing H by D changes the vibrational stabilization and slows ionization. If the four contributions were equal and independent, each would be .
None of those labeled C-H bonds is broken. The isotope effects support substantial carbocation character, although distinguishing a free cation from an intimate ion pair needs additional evidence.
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