Selective Synthesis of 2‐(4‐Aminoaryl)‐2‐(4‐pyranonyl)acetates and 2,2‐Bis(4‐aminoaryl)‐2‐(4‐pyranonyl)acetates from 2‐Diazo‐3,5‐dioxo‐6‐ynoates (ynones) and Aromatic Amines

On the basis of a tandem strategy, AgSbF6/Rh2(OAc)4/Ag3PO4‐mediated reaction of 2‐diazo‐3,5‐dioxo‐6‐ynoate (ynones) with N,N‐disubstituted anilines or aza‐aromatic hydrocarbons afforded a series of 2,2‐bis(4‐aminoaryl or aza‐aryl)‐2‐(4‐pyranonyl)acetates (or ketones) and 2‐(4‐aminoaryl or aza‐aryl)‐2‐(4‐pyranonyl)acetates (or ketones). For N‐allyl‐N‐substituted aniline, the corresponding cyclopropanation did not occurred. Disymmetric 2,2‐bis(4‐aminoaryl or aza‐aryl)‐2‐(4‐pyranonyl)acetates were also obtained in good yield from 2‐(4‐aminoaryl)‐2‐(4‐pyranonyl)acetates and N,N‐disubstituted anilines (or aza‐aromatic hydrocarbons) by C(sp3)–C(sp2) cross‐coupling reaction. AgSbF6/Ag3PO4 plays a key role in the C(sp3)–C(sp2) cross‐coupling reaction. This unique synthetic method for synthesis of two desired products starting from identical materials was proved to be efficient except for N‐substituted aniline. A novel AgSbF6/Ag3PO4/Rh2(OAc)4‐mediated tandem reaction for selective synthesis of 2‐(4‐aminoaryl)‐2‐(4‐pyranonyl)acetates (or ketones) and 2,2‐bis(4‐aminoaryl)‐2‐(4‐pyranonyl)acetates (or ketones) starting from 2‐diazo‐3,5‐dioxo‐6‐ynoates (ynones) 1 and N,N‐disubstituted aniline was developed. The corresponding cyclopropanation product was not observed when using N‐allyl‐N‐substituted aniline as substrate.