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The α‐arylation between cyanoacetate and 2‐(2‐bromophenyl)‐1H‐perimidine took place first catalyzed by CuI/L‐proline in the presence of NaHCO3, and then the amino on perimidine chemoselectively attacked the cyano group to undergo a nucleophilic addition, giving a series of 13‐aminoisoquinolino[2,1‐a]perimidine‐12‐carboxylate derivatives in good yields. [ABSTRACT FROM AUTHOR]

A series of ( E)- N-aryl-4 H-thiochromen-4-imines has been conveniently obtained through a cascade reaction between o-bromobenzothioamides and terminal alkynes. This novel approach probably involved an initial generation of benzothietane-2-imine intermidates via an intramolecular Ullmann reaction under CuI/L-proline cocatalysis and alkaline conditions followed by imine alkynylation, ring opening, and cyclization sequences to provide the unexpected 4 H-thiochromen-4-imines rather than isothiochromans.