First synthesis of optically pure selenuranes and stereoselective alkaline hydrolysis. Their application to asymmetric [2,3] sigmatropic rearrangement of allylic selenoxides

Article abstract of DOI:10.1016/S0040-4020(97)00546-2

The first synthesis of optically pure selenuranes 1 has been accomplished by utilizing 2-exo-hydroxy-10 bornyl group as a chiral ligand Complete retention of the configuration has been observed in alkaline hydrolysis of 1 to give selenoxides 2. The structure of 1 and 2 has been fully established by X-ray crystallography. [2,3] Sigmatropic rearrangement of allylic selenoxides 2 gave the corresponding allylic alcohols 3 with up to 88% enantiomeric excess (ee). The [2,3] sigmatropic rearrangement of allylic selenoxides 2 progresses predominantly via an endo transition state.