Schenck ene reaction

The hydroperoxides can be reduced to allylic alcohols or eliminate to form unsaturated carbonyl compounds.

Historically, four mechanisms have been proposed:[3] Experimental and computational studies show that the reaction actually proceeds via a two step no intermediate process.

The singlet oxygen is more likely to abstract hydrogen from the side with more C-H bonds due to favorable interactions in the transition state:[2] Very bulky groups, like the tertiary butyl group, will hinder hydrogen abstraction on that side.

The Schenck ene reaction is utilized in the biological and biomimetic synthesis of rhodonoids, yield Many hydroperoxides derived from fatty acids, steroids, and terpenes are also formed via the Schenck ene reaction.

For instance, the generation of cis-3-hexenal from linolenic acid: It must be noted, however, that this enzyme catalyzed path follows a different mechanism from the usual Schenck ene reaction.

The Schenck ene reaction
Four proposed intermediates of the Schenck ene reaction
Biological synthesis of rhodonoid A
Organic synthesis of rhodonoid E and F
Cis-3-hexenal is generated by conversion of linolenic acid to the hydroperoxide by the action of a lipoxygenase followed by the lyase-induced formation of the hemiacetal. [ 5 ]