Photocatalytic One-Pot Synthesis of Homoallyl Ketones via a Norrish Type i Reaction of Cyclopentanones
A photocatalytic synthesis of homoallyl ketones was achieved via a one-pot procedure starting from a Norrish Type I reaction of cyclopentanones, followed by a decatungstate-catalyzed hydroacylation of electron-deficient olefins by the resulting 4-pentenals. The site-selective formyl H-abstraction in the second step can be explained by radical polar effects in the transition state.
Intramolecular Addition of Alkoxy Radicals. Part 4. Reductive Cyclisation of Olefinic Hydroperoxides
Pent-4-enyl hydroperoxide reacts with reducing salts (FeX2, TiCl3) to afford tetrahydrofurfuryl compounds (halides or dimers) in high yield from the selective cyclisation of the pent-4-enyloxy radical.Analogous behaviour is observed for photolysis although the yields of cyclic products are lower.The photolysis of hex-5-enyl hydroperoxide does not yield cyclic products but these are observed when this hydroperoxide is reduced by FeCl2.It is suggested that metallic salts are able to complex the alkoxyl radicals thereby making them more electrophilic and hence more prone to cyclise.
Taillez, Bernard,Bertrand, Michele Paula,Surzur, Jean-Marie
p. 547 - 554
(2007/10/02)
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