69105-61-9Relevant academic research and scientific papers
Electron-transfer photochemistry of iminium salts. Olefin photoadditions to 2-phenyl-1-pyrrolinium perchlorate
Stavinoha, Jerome L.,Mariano, Patrick S.
, p. 3136 - 3148 (2007/10/10)
The photoaddition reactions of 2-phenyl-1-pyrrolinium perchlorate (2) and a variety of olefins have been investigated. Irradiation of methanolic solutions of 2 in the presence of the electron-rich olefins isobutylene, cyclohexene, butadiene, isopropenylcyclopropane, and methyl β,β-dimethylacrylate leads to formation of two types of addition products. One of these results from anti-Markovnikov addition of the components of methanol and the pyrrolinium salt across the olefinic π bond, generating a carbon-carbon bond to the pyrrolidine 2-position. The other corresponds to addition of the 2-phenylpyrrolidine unit across allylic C-H bonds of the olefins. Both reactions are explained by using electron-transfer mechanisms. Support for these mechanisms, which rationalize the nature of the reactions, their regiochemistry, and their stereochemistry, has come from studies with the electron-poor olefins methyl acrylate, acrylonitrile, and methyl methacrylate. Irradiation of 2 in the presence of these olefins leads to generation of 9-substituted 1-aza-6,7-benzospiro[4.4]non-6-ene products, results of [2 + 2] cycloadditions of the olefins to the C-1,C-2 π bond of the pyrrolinium salt phenyl ring. Fluorescence quenching studies have been conducted to gain further evidence in support of the mechanistic postulates.
PHOTOCHEMISTRY OF IMINIUM SALTS. ELECTRON TRANSFER MECHANISMS FOR SINGLET QUENCHING AND PHOTOADDITION OF N-ELECTRON DONATING ALCOHOLS AND ETHERS
Mariano, Patrick S.,Stavinoha, Jerome,Bay, Elliott
, p. 3385 - 3396 (2007/10/02)
Several aspects of past and current studies in the area of iminium salt photochemistry are discussed.Investigations of olefin-iminium salt photoaddition and photocyclization reactions are reviewed and conclusions about electron-transfer pathways for fluor
