129855-16-9Relevant academic research and scientific papers
The novel 1-aza-di-π-methane rearrangement of 1-substituted-1-aza-1,4- dienes promoted by DCA-sensitization
Ortiz, Maria J.,Agarrabeitia, Antonia R.,Aparicio-Lara, Santiago,Armesto, Diego
, p. 1759 - 1762 (1999)
Irradiation of a series of N-substituted-1-aza-1,4-dienes, using DCA as an electron transfer sensitizer, leads to the formation of the corresponding cyclopropane derivatives, in the second example of a rearrangement of the di- π-methane type that takes pl
Unexpected oxadi-π-methane rearrangement of β,γ-unsaturated aldehydes
Armesto, Diego,Ortiz, Maria J.,Romano, Santiago,Agarrabeitia, Antonia R.,Gallego, Mar G.,Ramos, Ana
, p. 1459 - 1466 (2007/10/03)
The oxadi-π-methane rearrangement (ODPM) is considered to represent the normal photochemical behavior of β,γ-unsaturated ketones in the triplet excited π,π* state. However, the usual photoreactivity reported for the majority of β,γ-unsaturated aldehydes i
Steric and Electronic Effects on the Photochemical Reactivity of Oxime Acetates of β,γ-Unsaturated Aldehydes
Armesto, Diego,Horspool, William M.,Gallego, Mar G.,Agarrabeitia, Antonia R.
, p. 163 - 170 (2007/10/02)
A general synthesis of 5-unsubstituted N-acetoxy 3,3-dimethyl-1-azapenta-1,4-dienes starting from 2-(1,3-dithian-2-yl)-2-methylpropanal is described.The influence of 5-phenyl, 4-phenyl, 5-cyclohexyl, 5-tert-butoxycarbonyl and 5,5-dicyclohexyl substitution on the outcome of the photochemical reactions of the oxime acetates of β,γ-unsaturated aldehydes has been studied with a view to proving or disproving the operation of a deactivating free rotor in the aza-di-?-methane rearrangement.The results obtained show that if the radical formed at C-5 can be stabilized by conjugation with an aryl group or by certain types of disubstitution then the aza-di-?-methane rearrangement takes place successfully.In any other situation the reaction fails.These results clearly show that the free rotor effect is not responsible for the failure of C-5 monosubstituted 1-aza-1,4-dienes to undergo the aza-di-?-methane rearrangement.
Unexpected Influence of Mono-phenyl Substitution on the Photochemistry of β,γ-Unsaturated Oxime Acetates
Armesto, Diego,Agarrabeitia, Antonia R.,Horspool, William M.,Gallego, Mar G.
, p. 934 - 936 (2007/10/02)
On irradiation of the oxime acetate of trans-2,2-dimethyl-4-phenylbut-3-enal (5) undergoes stereospecific aza-di-?-methane rearrangement to the oxime acetate of trans-2,2-dimethyl-3-phenylcyclopropanecarbaldehyde (7), while surprisingly the irradiation of the oxime acetate of 2,2-dimethyl-3-phenylbut-3-enal (10) follows a different reaction path and affords the oxime acetate of 4-methyl-3-phenylpent-3-enal (13) by a novel 1,3-migration pathway.
