Numerous polyketide natural products contain methyl ether functionality generated by either methoxymalonyl extender units or a selective O-methyl transferase associated with the polyketide synthase (PKS) gene cluster. In laboratory syntheses of such natural products, discrete steps for generating a hydroxyl stereogenic center and subsequent methylation are typically bracketed by additional protecting group manipulation steps. A fundamentally new tactic has been designed and developed. This methodology is capable of significantly simplifying the creation of functionality common to polyketide natural products by controlling the generation of a stereogenic center simultaneous with ether incorporation. In this thesis it is demonstrated that alkoxymethyl-protected homoallylic alcohols, under the treatment of iodine monochloride (ICl), undergo efficient alkyl ether (for example, methyl and benzyl) transfer to afford syn-1,3-diol monoalkyl ethers in good yields and with excellent diastereocontrol. The proposed reactive intermediate, bearing a chloromethyl functionality, was proven by NMR analysis. It was also observed that this intermediate has decent stability so that it's reactivity can be fully explored, allowing formation of a variety of synthetically useful fragments that can potentially be used in syntheses of complex molecules. The mechanism of the ether transfer reaction initiated by N-iodosuccinimide (NIS) has also been studied. By incorporating isotopic labels in the products followed by product analyses with NMR spectroscopy and comparison with the results from non-labeled experiments, relative rates of different pathways as well as the stereoselectivity preference within each has been investigated and identified. This stereoselective ether transfer methodology has also been successfully applied to the total synthesis of the family of all-syn isotactic polymethoxy natural products. Two syntheses examples of this product family are shown in this thesis. In addition, a generalized, convergent synthetic strategy aiming toward synthesis of any member of these polymer-like compounds is also proposed.