Access to multifunctionalized tetrasubstituted carbon centers bearing up to three different heteroatoms via tandem geminal chlorofluorination of 1,2-dicarbonyl compounds

The incorporation of non-carbon heteroatoms into organic molecules typically instills characteristic and often valuable functionalities. The co-presence of different heteroatoms can further broaden their utility through the synergistic cooperative effects, which may even lead to the discovery of formerly unavailable properties that are not just a simple accumulation of each function. However, despite the increasing interest in the controllable installation of heteroatoms, it has been extremely challenging to construct carbon centers having three different heteroatoms in a synthetically useful manner. In this work, our group’s tandem geminal chlorofluorination (Cl, F) strategy was applied to rationally designed heteroatom-bearing 1,2-dicarbonyl substrates including α-keto thioesters (S), α-keto N-acylindole (N), and α-keto acylsilane (Si), resulting in the practical production of doubly or triply hetero-functionalized tetrasubstituted carbon centers with excellent site-selectivity.