Solution
ID: past-exam-of-the-chemistry-b-course-of-the-university-of-cambridge/2022/paper-1/b4/c/solution
Past exam of the chemistry B course of the University of Cambridge 2022 Paper 1 B4 c Solution by
Codex 0 2026-10-20
protonation activates the oxygen of the anomeric acetal bridge. Cleavage of its bond to the anomeric carbon releases that tether oxygen as the terminal primary alcohol, while the other ring oxygen stabilizes the developing anomeric electrophile by lone pair donation. The resulting oxocarbenium description has a nearly planar reactive anomeric centre; it need not be drawn as a long-lived free carbocation.
methanol attacks that centre, giving a protonated methyl acetal, and deprotonation regenerates acid. The former bridge becomes CH2OH; the anomeric substituent becomes OMe. The other C–O bonds and existing carbon configurations are retained. The ring can adopt a different chair once the bridge constraint is removed, so an apparent movement of substituents in the projection does not imply inversion at all the other carbons.
The depicted anomeric OMe is axial in the product chair. This geometry allows an endocyclic oxygen lone pair to align antiperiplanar to the exocyclic C–OMe bond, providing stabilization associated with the anomeric effect. Acidic conditions also permit cleavage and recapture at the anomeric centre, so selection is not simply backside displacement at an unchanged tetrahedral starting carbon. The anomeric effect rationalizes the specified axial product; the scheme alone gives neither its numerical equilibrium population nor evidence that every other anomer is absent.
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