Manganese acid diester

Oxidation of the malonic acid diester 274 with manganese(lll) triacetate afforded both 275 and 276 but only in 35% overall yield <1995JOC6176>. 

The isolation of saturated and unsaturated acetic acid derivatives in the manganese(m) acetate oxidation of olefins has been reported earlier examples of this oxidation led solely to y-lactones. A one-step synthesis of aeo-di-carboxylic acid diesters has been reported, based on Kolbe electrolysis of oxalic and malonic half-esters in the presence of olefins, and is exemplified in Scheme 2. As part of a study of insect hormone activity, Kolbe electrolysis has been utilized in the preparation of aj9-unsaturated Cj4—Cj7 acid esters with a terminal quaternary alkyl group. The utility of liquid hydrogen fluoride in the Koch carbonylation of olefins has been descried, as has a general study of this reaction. ... 

Dihydropyridinones react with acetic acid or diethyl malonate to give partially reduced furo[3,2-f]pyridine derivatives in low to moderate yields (Scheme 34) <2002CHE368>. More highly reduced products are formed with the acid starting material in the presence of manganese triacetate than with the diester under the same conditions. 

The synthesis of several terpenoid natural lactones has been described. Butyrolactones are formed efficiently by the cyclization of hydroxy-acids, and acid olefin cyclization. The diester (123) has been converted independently into the isomeric lactones cinnamolide (124), and drimenin (125) (Scheme 71). Selective reduction of the a,/3-unsaturated ester was used in the latter case, whereas selective oxidation of the corresponding allylic alcohol with manganese dioxide was used in the former. Manganese dioxide has also been... 

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