Scope of the asymmetric intramolecular stetter reaction catalyzed by chiral nucleophilic triazolinylidene carbenes.
A highly enantioselective intramolecular Stetter reaction of aromatic and aliphatic aldehydes tethered to different Michael acceptors has been developed. Two triazolium scaffolds have been identified that catalyze the intramolecular Stetter reaction with good reactivity and enantioselectivity. The substrate scope has been examined and found to be broad; both electron-rich and -poor aromatic aldehydes undergo cyclization in high yield and enantioselectivity. The tether can include oxygen, sulfur, nitrogen, and carbon linkers with no detrimental effects. In addition, the incorporation of various tethered Michael acceptors includes amides, esters, thioesters, ketones, aldehydes, and nitriles. The catalyst loading may be reduced to 3 mol % without significantly affecting the reactivity or selectivity of the reaction.
de Alaniz
Javier Read
JR
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
Kerr
Mark S
MS
Moore
Jennifer L
JL
Rovis
Tomislav
T
D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D001547:Benzaldehydes / Q000737:chemistry*; D002384:Catalysis; D006838:Hydrocarbons / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D013237:Stereoisomerism; D014230:Triazoles / Q000737:chemistry*
D000447:Aldehydes; D000475:Alkenes; D001547:Benzaldehydes; D006838:Hydrocarbons; D014230:Triazoles; C030011:carbene; D008697:Methane