jz6b02632_si_001.pdf (3.08 MB)
Orbital Control of Photochemical Rearrangement of 4‑Aryl-1,1-dicyano-1-butenes through the Hyperconjugative Substitution on the Linker Chain
journal contribution
posted on 2016-11-14, 00:00 authored by Nobuo Matsuki, Yoshihisa Inoue, Tadashi MoriHyperconjugative
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.
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hyperconjugationbenzylic positionphotochemistryphotoreactivitystrengthLinker Chain Hyperconjugative interactionconformer distribution4-rolePhotochemical RearrangementHyperconjugative Substitutionallylic rearrangement productoutcomeArylsubstituentparent substrateanalysisOrbital Controlarylcontributionbond
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