Orbital Control of Photochemical Rearrangement of 4-Aryl-1,1-dicyano-1-butenes through the Hyperconjugative Substitution on the Linker Chain

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• 作者：Nobuo Matsuki ; Yoshihisa Inoue ; Tadashi Mori
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：December 15, 2016
• 年：2016
• 卷：7
• 期：24
• 页码：4957-4961
• 全文大小：324K
• ISSN：1948-7185

文摘

Hyperconjugative interaction was demonstrated to play a vital role in the photochemistry of 4-aryl-1,1-dicyano-1-butenes. Thus a simple substituent on the benzylic position effectively induced a new photoreactivity to afford an allylic rearrangement product that is not obtained for the parent substrate. The natural bond orbital analysis was employed to reveal the enhanced relative contributions of hyperconjugation in the excited state, which dramatically alter the photochemical outcomes not only by reducing the strength of the allylic/benzylic bond but more crucially by affecting the conformer distribution.