REGIOCHEMICAL CONTROL OF THE RING-OPENING OF 1,2-EPOXIDES BY MEANS OF CHELATING PROCESSES .5. SYNTHESIS AND REACTIONS OF SOME 2,3-EPOXY-1-ALKANOL DERIVATIVES

In order to study the effect of a remote polar functionality on the regiochemistry of the ring opening of aliphatic epoxides, the synthesis and some nucleophilic additions (methanolysis, azidolysis, and aminolysis) of suitable 2,3-epoxy-1-alkanol derivatives (epoxides trans-1a-d and cis-2) were carried out. The C-3 selectivity commonly observed when nonchelating ring opening conditions are used is lower than when the epoxides are allowed to react in the presence of metal ions (Li+, Mg2+, Zn2+) due to the probable intervention of bidentate-chelated intermediates in the latter case, and in some instances an almost complete C-3 regioselection is obtained. Under identical conditions involving chelation control, trans epoxide la shows higher C-3 selectivity than cis isomer 2. A free hydroxyl functionality is not necessary in order to observe chelation-controlled regioselectivity in the epoxides that we examined.