The Photochemical Reaction of Vinylaziridines and Vinylazetidines with Chromium(0) and Molybdenum(0) (Fischer) Carbene Complexes. Issue 5 (16th December 2013)

• Record Type: Journal Article
• Authors: Rivero, Alexandra R.; Fernández, Israel; Sierra, Miguel A.
• Is Part Of: Chemistry. Volume 20:Issue 5(2014)
• Page Start: 1359
• Page End: 1366
• Publication Date: 2013-12-16
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201302029
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The [5+2] and [6+2] cycloaddition reactions of vinylaziridines and vinylazetidines with ketenes generated photochemically from chromium(0) and molybdenum(0) Fischer carbene complexes have been investigated. These processes constitute a straightforward and efficient route to azepanones and azocinones, respectively. The peculiar electronic properties of the metalated ketenes allow for the introduction of electron‐rich substituents in the final cycloadducts, a difficult task using conventional organic chemistry procedures. The versatility of the process is demonstrated by using Cr⁰ Fischer bis(carbene) complexes as metalated bis(ketene) precursors. These species produce tethered bis(azepanone)s in a single step under mild reaction conditions. Density functional theory calculations point to a stepwise reaction pathway through the initial nucleophilic attack of the nitrogen atom of the aziridine on the metalated ketene, followed by ring closure of the zwitterionic intermediate formed.</p> </abstract>