The stereochemistry of the Grignard - ortho ester reaction revisited: Regioselective endocyclic cleavage in the reaction of grignard reagents with cis-2-methoxy-4-methyl-1,3-diloxane

Article abstract of DOI:10.1016/S0040-4039(97)00862-9

The reaction of cis-2-methoxy-4-methyl-1,3-dioxane (4) with Grignard reagents proceeds in a totally regioselective manner via rupture of the less congested C(2)-O(1) bond remote from the 4-methyl substituent. The analogous r-2-methoxy-cis-4,cis-6-dimethyl-1,3-dioxane (2) is totally inert to the action of Grignard reagents.