62073-81-8Relevant academic research and scientific papers
Stereochemistry of Epoxydation of Allylic and Homoallilyc Cyclohexene Alcohols
Kocovsky, Pavel
, p. 1759 - 1764 (2007/10/02)
The reactivity of cyclohexene-type allylic alcohols towards epoxidation reagents (peroxy acids and ButO2H with transition metal calalysts) is largely dependent on the magnitude of steric hindrance in the substrate molecules.With unhindered or slightly hindered allylic alcohols (4, 8 and 12) the reaction is dominated by the syn-stereodirecting effect of the hydroxy group which results in the exclusive or predominant formation of cis-epoxy alcohols.In contrast, this well established type of stereocontrol fails with sterically congested substrates (23, 26 and 27), which give trans-epoxy alcohols on m-chloroperbenzoic acid treatment while the transition metal-catalysed oxidation with ButO2H affords conjugated ketones as the sole products.The latter reaction can serve as a mild procedure for the selective oxidation of hindered allylic alcohols to α,β-unsaturated ketones.
