The Reaction of CO2 with a Borylnitrene: Formation of an 3‐Oxaziridinone. (21st September 2021)

• Record Type: Journal Article
• Authors: Bhagat, Virinder; Schumann, Julia; Bettinger, Holger F.
• Is Part Of: Angewandte Chemie. Volume 133:Number 43(2021)
• Page Start: 23296
• Page End: 23300
• Publication Date: 2021-09-21
• Subjects: matrix isolation -- nitrenes -- strained heterocycles; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202105171
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The reaction of a borylnitrene with carbon dioxide is studied under cryogenic matrix isolation conditions. Photogenerated CatBN (Cat=catecholato) reacts with CO2 under formation of the cycloaddition product CatBNCO2, a 3‐oxaziridinone derivative, after photoexcitation (>550 nm). The product shows Fermi resonances between the CO stretching and ring deformation modes that cause unusual 13 C and 18 O isotopic shifts. A computational analysis of the 3‐oxaziridinone shows this cyclic carbamate to be less strained than an α‐lactone or an α‐lactame. Abstract : Triplet borylnitrene 1 reacts photochemically ( λ >550 nm) under cryogenic matrix isolation conditions with CO2, which is known for its high thermodynamic and kinetic stability, to give a strained and unprecedented 3‐oxaziridinone motif 2 .