14525-88-3Relevant articles and documents
Adiabatic process of higher electronically excited states: luminescence from an excited state biradical generated by irradiation of benzophenone-substituted cyclopropanes
Matsui, Yasunori,Oishi, Toru,Ohta, Eisuke,Ikeda, Hiroshi
, (2017)
Adiabatic photochemical reactions of cyclopropanes possessing a benzophenone moiety (trans- and cis-5), which generate a luminescent excited biradical 16??*, were studied. Various photochemical and spectroscopic techniques were used for this purpose. Excitation (350 nm, n,π* band) of 5 at 77?K affords the lowest excited state 15* that undergoes intersystem crossing to form 35*, which deactivates through phosphorescence. In contrast, 295-nm excitation (π,π* band) of 5 affords the higher electronically excited state 15**, which undergoes adiabatic C–C bond cleavage reaction to form the excited biradical 16??* that luminesces at 630?nm. The results suggest that 5 follows 2 photoreaction modes depending on the excitation wavelength, a finding that disobeys Kasha's rule.
Silylium-Ion-Promoted Ring-Opening Hydrosilylation and Disilylation of Unactivated Cyclopropanes
Bonetti, Vittorio,Klare, Hendrik F. T.,Oestreich, Martin,Roy, Avijit,Wang, Guoqiang,Wu, Qian
supporting information, (2020/02/04)
A silylium-ion-promoted ring-opening hydrosilylation of unactivated cyclopropanes is reported. The reaction is facilitated by the γ-silicon effect, and the regioselectivity is influenced by various stabilizing effects on the carbenium-ion intermediates, including the β-silicon effect. The experimental observations are in accord with the computed reaction mechanism. The work also showcases the ability of silylium ions to isomerize cyclopropyl to allyl groups, and the resulting α-olefins engage in a silylium-ion-mediated disilylation with hexamethyldisilane.
THE MATRIX EFFECT ON STEREOSELECTIVITY OF OLEFIN CYCLOPROPANATION BY ARYLCARBENE
Tomioka, Hideo,Ozaki, Yasuji,Koyabu, Yasuhiro,Izawa, Yasuji
, p. 1917 - 1920 (2007/10/02)
Temperature studies of addition of phenylcarbene to styrene showed that stereoselectivity changed rather dramatically as the reaction phase changed.