Streamlined Assembly of Pyrimidinones via Wolff Rearrangement-Triggered [3 + 3] Cycloaddition of Alkynyl Diazoalkyl Ketones and 2-Aminoheteroarenes

We report a novel Wolff rearrangement/[3 + 3] cycloaddition cascade for efficient synthesis of pyrimidinone derivatives from alkynyl diazoalkyl ketones and aminopyridine or aminothiazole, achieving yields up to 99% with excellent regioselectivity. The protocol demonstrates remarkable efficiency and substrate tolerance, offering potential for nucleobase modification and the development of antimicrobial agrochemicals.