Allyl acetates dicarboxylation

Under these reaction conditions, cyclopentenone, allyl acetate, and butenyl acetate are dicarboxylated in high yields (equations 69-71).96... 

In this chapter, procedures for the polymerization of allyl acetate and related monocarboxylates of diallyl carbonate types, of diallyl phthalates, and of diallyl esters of other dicarboxylic acids are discussed. 

Allylic geminal dicarboxylates 285 are prepared by Pd-catalyzed reaction of propargyl acetate 284 with AcOH [104], Two products 287 and 288 are obtained from gem-allylic compounds 286, and 288 is an allylic ester and undergoes the second allylation. Several applications to asymmetric syntheses have been reported [48]. Reaction of 289 with dimethyl methylmalonate afforded 290 with 95% ee. 

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],... 

Z)-2-butenylene dicarbonate with dimethyl malonate gives a low yield (20—40%) of 2-vinylcyclopropane-l,l-dicarboxylate with up to 70% ee (Scheme 2-38) [54], Reaction with methyl acetoacetate or acetylacetone takes place in a different manner to give a dihydrofuran derivative (59% ee), which results from nucleophilic attack of enolate oxygen at the cyclization step, (c) Asymmetric elimination of an acetyl-acetate ester gives (R)-4-rerr-butyl-l-vinylcyclohexene of up to 44% ee (Scheme 2-39) [55]. (d) Palladium-catalyzed allylic silylation is also applied to asymmetric synthesis... 

Allylic gem.-diacetatesIn the presence of this Pd(0) catalyst, propargyl acetates react with acetic acid to form (H)-allylic g< m-diacetates in 55-79% yield (equation 1). Mixed gem-dicarboxylates can also be prepared. 

Access to a 1,4-dicarbonyl substrate has been realised in several ways. Examples include alkylation of imines with 2-alkoxy-allyl halides (equivalents of 2-halo-ketones),addition of /3-ketoester anions to nitroalkenes, followed by Nef reaction,and rhodium-catalysed carbonylation of 2-substituted acrolein acetals. The dialdehyde (as a mono-acetal) necessary for a synthesis of diethyl furan-3,4-dicarboxylate was obtained by two successive Claisen condensations between diethyl succinate and ethyl formate, as shown in the sequence below. 

Wang and Zhang used enantiopure cyclohexane-1,2-dicarboxylic chloride for the construction of the diacyl backbone [66]. Variation was observed through different diastereomers and aryl substituents. In the AHF of vinyl acetates and allyl amides, the all- R) diastereomer with 2-Cl-phenyl groups produced the best results. In the corresponding Rh(acac)(P-P) complex, a bite angle of 84.9° was calculated. 

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