Apiose, synthesis

Raphael and Roxburgh32 33 presented a second synthesis of DL-apiose (53) which started from 4-acetoxy-3-(acetoxymethyl)-l-ethoxy-1-butene (54). This synthesis also permitted the preparation of compound 56, a branched-chain sugar then presumed, erroneously, to be... 

Ethenediyl carbonate (l,3-dioxol-2-one vinylene carbonate, 417) is a readily available,270 versatile synthon having pronounced dienophilic properties.270-275 Diels-Alder adducts of 417 with 1,4-di-acetoxy-1,3-butadiene and furan were selectively converted into cy-clitols,256 257-275 and also served as precursors of DL-ribose derivatives258 (see Section IV, 2). Another possibility of applying 417 as an equivalent of a 1,2-dihydroxyethane unit has been demonstrated in a synthesis of racemic apiose. Photochemical cycloaddition of 417 to 1,3-diace-toxy-2-propanone (418) gave the oxetane derivative 419, which, on alkaline hydrolysis, afforded DL-apiose (420) in 23% yield.1... 

Acid chloride 611 was used320 as the substrate in the synthesis of L-apiose (53) (see Scheme 10). Further workM0,s n extended the use of... 

Incubation of D-[U-I4C]apiose with sterile Lemma minor (duckweed) produced less than 0.01% incorporation into the cell-wall polysaccharides.75 Most of the d-[U-i4C]apiose appeared as 14C02 some remained in solution in the medium and in the duckweed plants, primarily as degradation products of D-[U-14C]apiose, but not as the branched-chain sugar.75 There is an efficient synthesis of the [U-14C]apiose moiety of cell-wall polysaccharides from D-[U-14C]glucose under similar conditions.81 Of the plant tissues tested, only L. minor contained an enzyme system able to metabolize free apiose. Carrot, lettuce, and spinach tissues are unable to metabolize the free, branched-chain sugar.75... 

L. gifofoa,65-79-83 and P. crispum.m,7 , H2 H4,H5 In general, the results of these in vivo investigations, as well as those of in vitro biosynthetic studies, support the hypothesis proposed for the synthesis of D-apiose polysaccharides and apiin (4) by Grisebach and Dobereiner82 (see Fig. 1). They postulated that decarboxylation of a nucleoside... 

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... 

Synthesis of D-apiose from 1,2-O-isopropylidene- -L-threofuranose (28) has been accomplished.128 Oxidation with ruthenium tetraoxide... 

The chemical synthesis of L-apiose has been accomplished by starting with (a) L-threaric [(+)-tartaric] acid,19 (b) 2,3-0-... 

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