Allylic methoxyacetates

Transposition ofallylic methoxyacetates. Allylic methoxyacetates undergo re--rangement at room temperature on treatment with Eu(fod). Synfacial transfer of the ester rv up is observed. The rearrangement is efficient and not subject to steric hindrance, -ccause the metal coordinates with the tether atoms. 

As with inorganic solid catalysts, the most extensively studied system was acetic acid—ethanol [428,432,434,444—448]. Other alcohols used in kinetic studies were methanol [430,449,450], 2-propanol [438], 1-bu-tanol [429,431,433,451—458], allyl alcohol [459], 1-pentanol [434] and ethyleneglycol [460] besides acetic acid, the reactions of formic [450], propionic [443,461], salicylic [430,449], benzoic [453—457] and oleic acids [430,451—453] and of phthalic anhydride [462] have been reported. Investigation of a greater variety of reactants is reported in only one paper [463] six alcohols (C4, Cs and C8) and five acids (mainly dicarboxylic were studied. Transesterification kinetic studies were performed with ethyl formate [437,439,441], isobutyrate [437,439—441] acetate [402, 435—437,439—442], methoxyacetate [441] and acrylate [403,404,464, 465] the alcohols used were methanol [402,435,437,439—442,450],... 

Silyl-substituted ally methoxyacetate 1 undergoes the Claisen-Ireland rearrangement to diastereoselectively give optically active allylic silane 2 as exemplified by Scheme 5.1. The resulting silane is employed for asymmetric addition to both aliphatic and aromatic acetals 3a and 3b in the presence of MejSiOTf, giving rise to homoallylic ethers 4a and 4b, respectively, with high diastereo- and enantioselec-tivities [4]. The whole sequence of reactions is an example of 1,4- and 1,5-remote... 

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