Pérez-Ruiz Raúl, Sáez Jose A, Jiménez M Consuelo, Miranda Miguel A
Departamento de Química/Instituto de Tecnología Química UPV-CSIC, Universitat Politécnica de València, Camino de Vera s/n, 46022, Valencia, Spain.
Org Biomol Chem. 2014 Nov 14;12(42):8428-32. doi: 10.1039/c4ob01416b.
The radical anions of β-lactams, photogenerated in the presence of DABCO as an electron donor, undergo cycloreversion via N-C4 bond cleavage, back electron transfer and final C2-C3 bond cleavage, leading to olefins. The involved intermediates are 1,4-radical anions and 1,4-biradicals. The experimental observations are consistent with the results of DFT calculations.
在作为电子供体的三乙烯二胺（DABCO）存在下光生成的β-内酰胺自由基阴离子，通过N-C4键断裂、反向电子转移和最终的C2-C3键断裂进行环化反转，生成烯烃。涉及的中间体是1,4-自由基阴离子和1,4-双自由基。实验观察结果与密度泛函理论（DFT）计算结果一致。
