ASYMMETRIC SHARPLESS EPOXIDATION OF DIVINYLCARBINOL. erythro-D- AND -L-4-PENTENITOLS BY HYDROLYSIS OF REGIOISOMERIC EPOXY-4-PENTENOLS

Article abstract of DOI:10.1016/S0040-4020(01)96130-7

The asymmetric Sharpless epoxidation of divinylcarbinol (1), a secondary, achiral allylic alcohol, is described in detail.The epoxidation proceeds with high enantio-control and diastereo-selection.The resulting 1,2-epoxy-4-pentene-3-ols 2 are equilibrated to afford the internal epoxides 5.Hydrolysis of the regioisomers 2 and 5, respectively, furnishes opposite enantiomers of erythro-4-pentenitols 3 with high selectivity.Several derivatives of 3 are described, as well as result of a less stereoselective route - from D-glyceraldehyde acetonide (10) - providing NMR data of the threo series. - The acute toxicity of divinylcarbinol (1) is reported, along with the mutagenicity of 1, L-2 and L-5 as determined by Ames tests.