Solution

ID: past-exam-of-the-chemistry-course-of-the-year-4-of-the-natural-sciences-course-of-the-university-of-cambridge/2022/paper-2/section-i/35/c/iii/solution

Silver carbonate promotes deprotonation of the methylene group in methyl isocyanoacetate, giving the nucleophilic carbon . It adds to the alkyne carbon farther from the electron-withdrawing sulfone. This creates the new bond between the future pyrrole C2 and methyl-bearing C3 and leaves the vinyl anion at the sulfone-bearing carbon, future C4.
The vinyl anion then attacks the terminal carbon of the isocyanide intramolecularly, closing a five-membered ring with atom sequence C2–C3–C4–C5–N. Proton transfers place one of the starting methylene hydrogens on nitrogen and the other on C5, giving an aromatic pyrrole. The product has COMe at C2, methyl at C3 and the retained arylsulfonyl group at C4. This is an addition–cyclization–aromatization sequence: the isocyanide contributes both ring nitrogen and the otherwise unsubstituted ring carbon, rather than acting as a cyanide leaving group.

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