Remember how it was …? A mechanistic explanation for the chiral-memory effect in NorrishYang photoreactions has been obtained by computing the reaction pathway (see figure) at the ab initio level. The results show that both the ultrafast excited-state decay, which occurs at a conical intersection (CI), and the specific hydrogen-bonded structure of the primary diradical intermediate determine the high stereoselectivity of the reaction.
Sinicropi, A., Barbosa, F., Basosi, R., Giese, B., Olivucci, M. (2005). Mechanism of the Norrish-Yang Photocyclization Reaction of an Alanine Derivative in the Singlet State: Origin of the Chiral Memory Effect. ANGEWANDTE CHEMIE. INTERNATIONAL EDITION, 44(16), 2390-2393 [10.1002/anie.200461898].
Mechanism of the Norrish-Yang Photocyclization Reaction of an Alanine Derivative in the Singlet State: Origin of the Chiral Memory Effect
SINICROPI, ADALGISA;BASOSI, RICCARDO;OLIVUCCI, MASSIMO
2005-01-01
Abstract
Remember how it was …? A mechanistic explanation for the chiral-memory effect in NorrishYang photoreactions has been obtained by computing the reaction pathway (see figure) at the ab initio level. The results show that both the ultrafast excited-state decay, which occurs at a conical intersection (CI), and the specific hydrogen-bonded structure of the primary diradical intermediate determine the high stereoselectivity of the reaction.
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https://hdl.handle.net/11365/24087
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