Diketones dicarboxylic acid anhydrides

Ozone trimethyl phosphite Acyl peroxides from a-diketones Dicarboxylic acid anhydrides from o-quinones via cyclic acyl peroxides... 

Hydrogen peroxide Dicarboxylic acid anhydrides from cyclic a-diketones... 

Figure 14.7. Chemical structures of some chelators and enhancers used in time-resolved fluoroimmunoas-says 1, isothiocyanatophenyl-EDTA 2, Ari-p-(isothiocyanatobenzyl)-diethylenetriaminetetraaceticacid 3, diethylenetriaminepentaacetic anhydride (DTPA) 4, Tb3+-DTPA-/t-aminosalicylic acid S, Eu3+-pyridine-bisfmethylaminodiacetic acid) 6, benzoyltrifluoroacetone (BTA, a /i-diketone) 7, trifluoroacetylacetone (a/jt-diketone) 8,4,7-bis(chlorosulfonylphenyl)-l,10-phenanthroline-2,9-dicarboxylic acid (BCPDA).

The last synthesis to evolve which is due to Ito and his coworkers is interesting in that it relies on a stereospecific skeletal rearrangement of a bicyclo[2.2.2]octane system which in turn was prepared by Diels-Alder methodology (Scheme XLVIII) Heating of a toluene solution of cyclopentene 1,2-dicarboxylic anhydride and 4-methylcyclohexa-l,4-dienyl methyl ether in the presence of a catalytic quantity of p-toluenesulfonic acid afforded 589. Demethylation was followed by reduction and cyclization to sulfide 590. Desulfurization set the stage for peracid oxidation and arrival at 591. Chromatography of this intermediate on alumina induced isomerization to keto alcohol 592. Jones oxidation afforded diketone 593 which had earlier been transformed into gymnomitrol. 

---