Oxygen nucleophiles, ring opening

The primary type of epoxide reaction remains the nucleophilic ring-opening reaction. The ring opening reactions of epoxides with oxygen nucleophiles represents an important method for the synthesis of differentially O-substituted 1,2-diols. The ring opening of epoxides with... 

Some noteworthy intramolecular nucleophilic ring openings have been reported in the recent literature, which can be used to prepare functionalized heterocycles of synthetic interest. For example, the highly oxygenated epoxide 100 undergoes rearrangement induced by boron trifluoride etherate, whereby anchimeric assistance from the pendant phenylthio substituent leads to an intermediate episulfonium ion 101 which subsequently suffers 5-e o-tet cyclization to form the tetrahydrofiiran derivative 102 <03TL5547>. 

Nucleophilic ring opening involving attack at oxygen occurs upon treatment of bicyclic peroxides such as 70 with either vinyllithium or vinylmagnesium bromide to give 71 in 80-90% yields (Equation 6) <1996TL6635>. 

Nucleophilic Ring-opening Reactions of Oxirans.—Reactions with Oxygen and Nitrogen Nucleophiles. A series of papers have appeared that deal with the reactions of lower aliphatic alcohols (R OH) with (120 = Me) to yield (121 ... 

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