Gold-Catalyzed Synthesis of Functionalized Pyridines by Using 2H-Azirines as Synthetic Equivalents of Alkenyl Nitrenes.

Agnes Prechter (1, 2) , Guilhem Henrion (2, 1) , Pierre Faudot Dit Bel (1, 2) , Fabien Gagosz (1, 2)

1 DCSO - Laboratoire de synthèse organique
2 X-DEP-CHIM - Département de Chimie de l'École polytechnique

2H-Azirines are easily synthesized from the corresponding ketones and, despite possessing a CN bond embedded in a strained three-membered cycle, they are sufficiently stable to be isolated, stored, and manipulated. 2H-Azirines can be regarded as valuable synthetic equivalents of alkenyl nitrenes, however, reactions capitalizing on the cyclic strain of the heterocyclic motif and involving the cleavage of the CN single bond remain surprisingly limited. A gold-catalyzed reaction that allows the formation of polysubstituted functionalized pyridines from easily accessible 2-propargyl 2H-azirine derivatives was developed. This transformation, which corresponds to an unprecedented intramolecular transfer of an alkenyl nitrene to an alkyne, proceeds with low catalyst loading, is efficient, and exhibits a high functional-group tolerance and a wide substrate scope.

Domains: Organic chemistry

Agnes Prechter, Guilhem Henrion, Pierre Faudot Dit Bel, Fabien Gagosz. Gold-Catalyzed Synthesis of Functionalized Pyridines by Using 2H-Azirines as Synthetic Equivalents of Alkenyl Nitrenes.. Angewandte Chemie International Edition, 2014, 53 (19), pp.4959-63. ⟨10.1002/anie.201402470⟩. ⟨hal-01001934⟩