Peroxy malonates

Peroxy esters of malonic and succinic acids have been subjected to thermal decomposition and the kinetic data are given in Table 110. A two-bond homolysis... 

THERMAL DECOMPOSITION OF PEROXY ESTERS OF MALONIC AND SUCCINIC ACIDS AT... 

An attractive alternative synthesis was likewise developed by Firmenich. [105, 106] Pentylcyclopentenol, is enzymatically transesterified with dimethyl malo-nate, whereby the (S)-enantiomer remains unaltered, but this can be racemised in the presence of sulfuric acid. The malonate is converted into an allylsilylke-tene acetal, which is then subjected to a Claisen rearrangement this proceeds under the control of the aUyl alcohol at relatively low temperatures and with high stereoselectivity. After decarboxylation, there follows the key step in the synthesis a n-selective epoxidation with highly electrophilic peroxy-acids, such as peroxytrifluoroacetic acid. The high n-selectivity arises from electrostatic effects between the more electron-rich r-side of the douple bond and the partial... 

The peroxy compounds have high energy contents. The weakness of the 0—0 bond (35 kcal/mole) (53) is a reflection of the unfavorable O (hard) and O (soft) combination. Diacyl peroxides, for example, react vigorously with soft donors such as phosphines (54, 55). This deoxygenation process has been applied to the synthesis of the highly strained malonic anhydrides (56). 

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