L- -Glyceraldehyde acetonide

Fluorofuranose precursors are prepared via Horner-Emmons reaction on L-glyceraldehyde acetonide (Figure 6.11). Due to the allylic position of the base, these compounds are much more unstable than the related saturated molecules (cf. Figure 3.17, Chapter 3). The presence of the fluorine atom enhances the hydrolytic stability of these compounds. Some of these molecules have good antiviral activities on infected cells. 

Alternate Name (5)-glyceraldehyde acetonide, L-glyceraldehyde acetonide, 2,3-0-isopropylidene-L-glyceraldehyde. 

A related strategy starting from a uronic acid was reported to construct the core stmcture of zaragozic acid [122,123]. The key point was the formation of the C4-C5 bond using aldol condensation. As shown in Scheme 11.40, methyl uronate 168 was first treated with KHMDS at —100°C, and then treated with a premixed solution of cerium chloride and (l )-glyceraldehyde acetonide to give the expected aldol as a mixture of diastereoisomers in a yield of 65 to 70%. 

Wittig olefination of D- or L-glyceraldehyde acetonide with Ph3P=CHCHO gives, after reduction of the enal with diisobutylaluminum hydride, ( )-allylic alcohols that undergo Katsuki-Sharpless enantioselective epoxidation [255,256,257]. The method has been applied to prepare D-arabinitol (=D-lyxitol) and ribitol (a meso alditol) and D-arabinitol (or xylitol, another meso alditol) [258],... 

Optically pure glyceraldehyde acetonides are widely used in the synthesis of enantiomerically pure compounds (EPC synthesis).1 2 3 4 5 Whereas D-(R)-glyceraldehyde acetonide is easily obtained from the inexpensive D-mannitol,6 7 there are only a limited number of practical syntheses of the enantiomeric L-(S)-glyceraldehyde acetonide.8 9 Difficulties arise from different sources 1) availability of the starting material diisopropylidene-L-mannitol 2) length of the synthesis 10 3) nature of the reactants used mercury acetate, mercaptans, lead tetraacetate, ozone at -78°C, 4) moderate yields.11 14... 

L-(S)-Glyceraldehyde acetonide 1,3-Dioxolane-4-carboxaldehyde, 2,2-dimethyl-, L- (8) 1,3-Dioxolane-4-carboxaldehyde, 2,2-dimethyl-, (S)- (9) (22323-80-4) Sodium (meta)periodate Periodic acid, sodium salt (8,9) (7790-28-5) 5,6-0-lsopropylidene-L-gulono-1,4-lactone L-Gulonic add, 5,6-0-(1-methylethylidene)-, y-lactone (11) (94697-68-4)... 

Fraisse, P, Hanna, 1, Lallemand, J Y, Prange, T, Ricard, L, An approach to the bicyclic core of the zaragozic acids via the aldol reaction between methyl (a-D-xylofuranoside)uronate and D-(i )-glyceraldehyde acetonide, Tetrahedron, 55, 11819-11832, 1999. 

Hubschwerlen, C, A convenient synthesis of L-(5)-glyceraldehyde acetonide from L-ascorbic acid. 

Kusakabe, M, Sato, F, Stereoselective synthesis of D-erythrose and D-threose derivatives from D-glyceraldehyde acetonide and their reactions with l-(trimethylsiyl)vinyl cuprate reagent. Synthesis of allitol acetate, Chem. Lett., 1473-1476, 1986. 

The Merck Frosst group used the acetonide of L-glyceraldehyde 34 readily obtained from L-arabinose as a starting material for the olefin 35 (Scheme... 

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