RING-OPENING SN2' REACTIONS OF 7-OXANORBORNENES BY ORGANOLITHIUM REAGENTS. REGIO- AND STEREOSPECIFIC SYNTHESIS OF SUBSTITUTED CYCLOHEXENEDIOLS

Article abstract of DOI:10.1016/S0040-4020(01)81475-7

The nucleophilic SN2' bridge opening of 7-oxabicyclo<2.2.1>hept-5-en-2-ols with organolithium reagents occurs in a regio- and stereospecific fashion to produce 6-substituted-cyclohex-4-en-1,3-diols, regardless of the stereochemistry at C-2.A free alcohol functionality is necessary to attain complete regiocontrol of the process.The methodology is utilized to prepare an optically pure cyclohexene derivative, (+)-(1S,3S,6R)-6-n-butyl-3-methyl-cyclohex-4-en-1,3-diol (5b), as a model system.