Synthesis of D-Apiose and Its Analogs

Naturally occurring apiose appears to be D-apiose.18,20,122 DL-Apiose was first chemically synthesized17 in 1955. 

Chemical synthesis of D-apiose has been accomplished by a number of methods.18,20,63 A one-step conversion of the branched-chain pentose 4-C-(hydroxymethyl)-D-threo-pentose (9) yielded18 

HOHjC—C—CIljOH PhCHaOCH HCOH HCOH CH8OH 

Khalique20 synthesized D-apiose by treating /ceto-D-fructose pen-taacetate (18) with diazomethane, and deacetylating the product (19) with barium methoxide to give epoxide (20), which, by oxidation with 2 equivalents of sodium metaperiodate, was converted into a syrupy epoxy-aldehyde (21), characterized as its crystalline phenylos-azone. Hydrolysis of compound 21 with aqueous acid produced 

D-apiose (1), characterized by optical rotatory data, paper-chromatographic mobility, and the melting point of the (p-bromophenyl)-osazone and the diisopropylidene acetal.20 

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