Experimental and Theoretical DFT Study on Synthesis of Sterically Crowded 2,3,3,(4)5‐Tetrasubstituted‐4‐nitroisoxazolidines via 1,3‐Dipolar Cycloaddition Reactions Between Ketonitrones and Conjugated Nitroalkenes |
| |
Authors: | Radomir Jasiński Kamila Mróz Agnieszka Kącka |
| |
Affiliation: | Institute of Organic Chemistry and Technology, Cracow University of Technology, Cracow, Poland |
| |
Abstract: | 1,3‐Dipolar cycloaddition reactions between ketonitrones ( 1a , 1b , 1c , 1d , 1e ) and β‐substituted nitroalkenes ( 2a , 2b , 2c , 2d ) proceed under mild conditions, with complete regioselectivity, and lead with high yields to sterically crowded 2,3,3,5‐tetrasubstituted‐4‐nitroisoxazolidines ( 3a , 3b , 3c , 3d , 3e , 3f ). Reaction course may be interpreted on the basis of nature of local, nucleophile–electrophile interactions. Moreover, density functional theory (DFT) simulations of reaction paths suggest that these reactions should be considered as polar, “one‐step two‐stage” cycloadditions. Subsequently, it has been found that similar reactions between ketonitrones and α‐substituted nitroalkenes do not allow to obtain the expected 2,3,3,4‐tetrasubstituted‐4‐nitroisoxazolidines. |
| |
Keywords: | |
|
|