1.2- O-Isopropylidene-D-glyceraldehyde

In the presence of water, 2,3-O-isopropylidene-D-glyceraldehyde forms the highly water soluble hydrate 1. Failure to dry the reaction and reslurry the filter cake results in loss of about 10% yield. 

A higher-branched sugar, 35, was synthesized from 262, obtained by the Grignard reaction of 2,3-O-isopropylidene-D-glyceraldehyde by conversion of the methylene derivative 263 into 264 with osmium... 

These reactions convert 2,3-O-isopropylidene-D-glyceraldehyde (1) into 2,3-diacetyl-D-erythronolactone (3). 

F. L. Tejero, T. Ready access to enantiopure 5-substituted 3-pyrrolin-2-ones from N-benzyl-2,3-O-isopropylidene-D-glyceraldehyde nitrone. Tetrahedron Asymmetry 1998, 9,1759— 1769. 

A synthesis of (+)-KDO has been reported by Martin and Zinke [118], which relies on the highly stereoselective addition of 2-furyllithium to 2,3-O-isopropylidene-D-glyceraldehyde R)-24. 

Condensation of 2,3-O-isopropylidene-D-glyceraldehyde-A -benzylimine 211 with 2-(tri-methylsilyloxy)furan in the presence of a Lewis acid generates a mixture of butenolides 212 that is converted into D-nZ 6>-A, A -diprotected derivative 213 in 68% yield (Scheme 13.67) [119]. Dihydroxylation of 213, followed by diol protection and lactone reduction, furnishes the 5-amino-5-deoxyheptose derivative 214. Hydrogenolysis in MeOH generates 215 and its deprotection furnishes enantiomerically pure l,5-dideoxy-l,5-imino-D-g/yc r6>-D-a//6>-heptitol 216 [120]. 

A. Dondoni, J. Orduna, and P. Merino, Construction of all 0-alkoxy D-tetrose and D-pentose stereoisomers from 2,3-O-isopropylidene-D-glyceraldehyde using 2-(trimethylsilyl)thiazole as a formyl anion equivalent. Synthesis p. 201 (1992). 

To a solution of 2,3-O-isopropylidene-D-glyceraldehyde (12.6 g, 97 mmol) in furan (20 mL), chloroacetic acid (5.7 g, 60 mmol) dissolved in furan (20 mL) was added and the mixture was refluxed for 8 h. After 12 h at room temperature saturated aqueous NaHCOj solution (50 mL) was added and the product was extracted with ether (3 x 100 mL). Combined ether extracts were dried (MgSO,j), concentrated to dryness, and the residue was chromatographed on a silica gel column with tight petroleum-ether-methanol (6 4 0.5) to yield IR R- and lS,2f -l-C-(2-furyl)-2,3-0-isopropylidcne-glycerols 1 (95 5,7.0 g, 36.5%). 

O-isopropylidene-D-glyceraldehyde in a highly stereoselective manner giving, after alcohol protection, imine hydrolysis and amine protection, a D-arabinopentonate derivative [231]. Further elaboration leads to 2-acetamido-2-deoxy-D-arabinose. In a similar fashion, starting from (5)-atrolactic acid, 2-acetamido-2-deoxy-D-ribose has been prepared [232,233,234,235, 236]. 

Synthesis by carbon-carbon bond formation between an acyclic sugar derivative and the benzothiazole ring system has also been utilized for the synthesis of these C-nucleosides. In one report, 2,3-O-isopropylidene-D-glyceraldehyde (61) was coupled with 2-trimethylsilylbenzothiazole to afford the A-nucleoside 185 as an intermediate, which underwent a 1,2-shift of the alditolyl chain to produce the C-nucleoside 186 (85TL5477) (Scheme 55). 

The Knoevenagel reaction of 2,3-O-isopropylidene-D-glyceraldehyde with active methylene compounds has led to derivatives of D-fructose and D-sorbose (Scheme 6). Similar condensations with other 3-dicarbonyI compounds led to furan derivatives on acidic hydrolysis. In the self-condensation of D-fructose... 

In the area of 3-ulosonic acids, the pentose derivative (17) has been prepared from 2,3-O-isopropylidene-D-glyceraldehyde by use of diazoacetic ester,and... 

The 2-C-methylene derivatives (17) are available by condensation of 1,1-di-methoxyprop-2-en-2-yl-lithium with 2,3-O-isopropylidene-D-glyceraldehyde, with the erythro-isomcx predominating over the t/zreo-isomer (7 3). Methanolysis of (17) afforded methyl 2-deoxy-2-C-methylene-j3-D-e/ yf ro-pentopyranoside and methyl 2-deoxy-2-C-methylene-0 -L-r)i/ eo-pentopyranoside from the erythro-... 

Contrary to an earlier report (Vol. 22, p. 2) that 2,3-O-isopropylidene-D-glyceraldehyde reacts with phenyl vinyl sulphide to give an oxetane, it has now been shown that 2,3 4,5-di-0-isopropylidene-aWe/ryrfo-D-arabinose reacts to give the product of acetal migration (114) (Scheme 14) from which the potentially useful thioglycoside (115) was obtained. ... 

More modest asymmetric induction is obtained in the reactions of magnesium enolates of dihalogenoacetates with 2,3-O-isopropylidene-D-glyceraldehyde, which give P-hydroxy-esters with a ratio of erythro threo isomers of 7 3. ... 

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