[1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1‐Pyrrolines through Olefination. Issue 19 (6th April 2018)

• Record Type: Journal Article
• Authors: Kanchupalli, Vinaykumar; Katukojvala, Sreenivas
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 19(2018)
• Page Start: 5433
• Page End: 5437
• Publication Date: 2018-04-06
• Subjects: annulation -- carbenoids -- diazoenals -- olefinations -- pyrrolines; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201801976
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal‐functionalized 1‐pyrroline derivatives was developed. The reaction involves a novel rhodium‐catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1‐pyrrolines. Structural diversification of the enal‐functionalized 1‐pyrrolines resulted in the biologically important pyrrolidine‐fused oxaziridine, amino acid derivatives, and a 6‐azabicyclo[3.2.1]octane motif present in polycyclic alkaloids. Abstract : A rhodium‐catalyzed olefination of diacceptor diazo compounds with vinyl azides to give electrophilic terminal olefins was developed. This method was demonstrated in a Rh II ‐catalyzed [1+1+3] annulation of diazoenals with vinyl azides to give enal‐functionalized substituted 1‐pyrrolines. Diverse pyrroline and pyrrolidine heterocycles were synthesized by using this method.