DL-Apiose

Addition of the elements of ethyl hypobromite to XXX gave an acetal-bromo derivative (XXXII) which was converted to DL-apiose (XXXIII) through the following series of reactions. 

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... 

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

The simple synthesis of DL-apiose, completed by Ishido, also makes use of 6 as the substrate. Photochemical cycloaddition of 1,3-diacetoxy-2-propanone to 6 gave an oxetane derivative 13, which on alkaline hydrolysis afforded apiose in 23% overall yield. 

Y. Araki, J. Nagasawa, and Y. Ishido, "Synthesis of DL-apiose derivatives by photochemical cycloaddition of 1,3-dihydroxypropanone-2, J. Chem. Soc., Perkin /, 12 (1981). 

Deoxy-3-C-hydroxymethyl-DL-lyxose and ribose derivatives have been synthesized from 2-methyl-3-furoic acid by a procedure analogous to that used for preparing DL-apiose from 3-furoic acid (see Vol. 7, p. 115). L-My-carose (5) has also been prepared from non-carbohydrate precursors by the... 

The formose reaction continues to attract attention. Detailed product analysis has been carried out on the autocatalytic condensation of formaldehyde using capillary g.l.c.-mass spectrometry. In addition to the previously reported sugars, pent-2-uloses, hex-3-uloses, DL-apiose and other branched hexoses were found. 

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