Mechanism of the N-cyclopropylimine-1-pyrroline photorearrangement.
We present here a combined experimental and computational investigation into the photorearrangement of N-cyclopropylimines to yield pyrrolines. We show that the photochemistry, regiochemistry, and stereochemistry of the reaction can be understood in terms of a mechanism involving barrierless evolution in three different (S(2), S(1), S(0)) singlet states and sequential decay through two different (S(2)/S(1), and S(1)/S(0)) conical intersection funnels. We provide evidence that the reaction mechanism involves the generation of a nonequilibrated (i.e., transient) excited state diradical, whose decay can lead not only to pyrrolines but also to cyclopropylimine isomers. It is concluded that the reaction outcome depends on the details of the structure of such transient diradical and on the nature of the dynamics of its decay through the S(1)/S(0) conical intersection.
Sampedro
Diego
D
Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, Unidad Asociada al C.S.I.C., Madre de Dios, 51, E-26006 Logroño, Spain. diego.sampedro@dq.unirioja.es
Soldevilla
Alberto
A
Rodríguez
Miguel A
MA
Campos
Pedro J
PJ
Olivucci
Massimo
M