REACTION OF 2-METHOXY-1,3-DIOXANE WITH GRIGNARD REAGENTS: REAGENT-SUBSTRATE COMPLEXATION AND STEREOELECTRONIC CONTROL.

Article abstract of DOI:10.1016/S0040-4039(01)90150-9

The stereoelectronically controlled reaction of 2-methoxy-1,3-dioxane (1) with Grignard reagents does not follow the course suggested by the behavior of anancomeric models for the conformational isomers of 1.Treatment of 1 with RMgX leads to the predominant formation of acid labile 3-(1'-methoxyalkoxy)-1-propanols, derived from endocyclic cleavage of the ring C-O bond, and only minor amounts of the expected 2-R-1,3-dioxanes.