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Synthetic Diversity from a Versatile and Radical Nitrating Reagent.
- Source :
-
Chemistry - A European Journal . 10/8/2019, Vol. 25 Issue 56, p12929-12939. 11p. - Publication Year :
- 2019
-
Abstract
- We leverage the slow liberation of nitrogen dioxide from a newly discovered, inexpensive succinimide‐derived reagent to allow for the C−H diversification of alkenes and alkynes. Beyond furnishing a library of aryl β‐nitroalkenes, this reagent provides unparalleled access to β‐nitrohydrins and β‐nitroethers. Detailed mechanistic studies strongly suggest that a mesolytic N−N bond fragmentation liberates a nitryl radical. Using in situ photo‐sensitized, electron paramagnetic resonance spectroscopy, we observed direct evidence of a nitryl radical in solution by nitrone spin‐trapping. To further exhibit versatility of N‐nitrosuccinimide under photoredox conditions, the late‐stage diversification of an extensive number of C−H partners to prepare isoxazolines and isoxazoles is presented. This approach allows for the formation of an in situ nitrile oxide from a ketone partner, the presence of which is detected by the formation of the corresponding furoxan when conducted in the absence of a dipolarophile. This 1,3‐dipolar cycloaddition with nitrile oxides and alkenes or alkynes proceeds in a single‐operational step using a mild, regioselective, and general protocol with broad chemoselectivity. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 09476539
- Volume :
- 25
- Issue :
- 56
- Database :
- Academic Search Index
- Journal :
- Chemistry - A European Journal
- Publication Type :
- Academic Journal
- Accession number :
- 139015404
- Full Text :
- https://doi.org/10.1002/chem.201902966