Solution

ID: past-exam-of-the-chemistry-course-of-the-year-4-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-1/8/a/ii/solution

Let , with its O and N donors available for lithium coordination. A plausible symmetric tetramer has a LiO cubane-type core, with alternating Li and phosphoryl O vertices and an additional enamide N donor attached to each Li. The O,N-chelating Ligand in coordination chemistry can be arranged equivalently around the aggregate, consistent with one Li environment. This is a connectivity model, not a uniquely reconstructed diffraction structure.
The initially formed nitrile-addition product has an acidic group next to the phosphine oxide. Transfer of one of these protons to the nitrile-derived N gives a delocalized lithiated enamide, reinforced by O,N coordination and organolithium aggregation. The organic framework becomes .
Assign to the vinylic CH and to NH. Each integrates to one proton, as required after hydrogen migration. Their singlet appearance does not mean that the original carbon has become a freely rotating, equivalent-proton methylene group.
Figure 1.
Enamide formation and plausible lithium–oxygen aggregation connectivities
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