10.1021/acs.jpclett.6b02632.s001
Nobuo Matsuki
Nobuo
Matsuki
Yoshihisa Inoue
Yoshihisa
Inoue
Tadashi Mori
Tadashi
Mori
Orbital Control of Photochemical Rearrangement of
4‑Aryl-1,1-dicyano-1-butenes through the Hyperconjugative Substitution
on the Linker Chain
American Chemical Society
2016
hyperconjugation
benzylic position
photochemistry
photoreactivity
strength
Linker Chain Hyperconjugative interaction
conformer distribution
4-
role
Photochemical Rearrangement
Hyperconjugative Substitution
allylic rearrangement product
outcome
Aryl
substituent
parent substrate
analysis
Orbital Control
aryl
contribution
bond
2016-11-14 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Orbital_Control_of_Photochemical_Rearrangement_of_4_Aryl-1_1-dicyano-1-butenes_through_the_Hyperconjugative_Substitution_on_the_Linker_Chain/4246709
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.