Threitol 1,4-anhydro

Hartman and R. Barker synthesized 1,4-anhydroerythritol (3) by the saponification of 1-O-p-tolylsulfonyl-D-erythritol (1). The reaction apparently proceeded by direct reaction of the 4-hydroxyl group with the 1-p-tolylsulfonoxy group, and not through the intermediate formation of the 1,2-anhydride, which would have afforded the epimer, namely, 1,4-anhydro-D-threitol (2). Similarly, 1-O-p-tolylsulfonyl-D-threitol gave 1,4-anhydro-D-threitol (2). 

However, saponification of 2-O-p-tolylsulfonyl-L-erythritol or of 2-O-p-tolylsulfonyl-D-threitol did not furnish any 1,4-anhydro compounds, but only the respective tetritol. 

Erythritol and L-threitol have also been dehydrated by means of 50% sulfuric acid at 120° to the corresponding 1,4-anhydrides.6 On heating erythritol in the presence of a small proportion of a xylene-sulfonic acid at 130-150° under vacuum, an 89% yield of 1,4-anhydro-DL-erythritol was obtained.7... 

Trifluoroacetic acid hydrolysis of the isopropylidene protecting group in 79 without loss of the tosyl group provides (25,3 5)-1-0-tosyl-L-threitol (116), which can be cyclized with basic resin to afford (25,3 S)-l,4-anhydro-L-threitol (117) in good overall yield. Treating 117 with triphenylphosphine in pyridine affords the chiral diphosphinite diphin (118), which has been utilized as a ligand in asymmetric hydrogenation, hydrocyanation, and hydroformylation reactions [48] (Scheme 26). 

Substrates of this type were utilized for the synthesis of alditols. Schneider and co-workers prepared from trans and cis 2-buten-1,4-diols 2,3-anhydro-DL-erythritol (54) and -threitol (55) by direct epoxidation with peroxybenzoic acid. This method of epoxide formation failed in the case of 2 ,4 -hexadiene-l,6-diol from the 2Z,4Z isomer the corresponding diepoxide (57) was obtained in a 2% yield only. However, from 1,6-dibromo-and 1,6-dibenzyloxycarbonyloxy-2 ,4 -hexadienes the corresponding derivatives of 2,3 4,5-dianhydro-DL-gal-actitol (56) could be obtained in moderate yields. Compounds of this type are active against some forms of sarcoma. 

Erythritol gives a sirupy 1,4-anhydroerythritol (1,4-erythritan) on heating with dilute sulfuric acid or with phosphoric acid and subsequent saponification of the monophosphate ester 60). Dehydration of L-threitol by heating with 50% sulfuric acid yields the crystalline 1,4-anhydro-L-threitol (1,4-L-threitan) 61). 

Anhydroerythritol has been converted into 1,4-anhydro-DL-threitol by chloride displacement of a toluene-p-sulphonyloxy-group. The dimethyl [2]-cryptand (59) has been obtained in a five-step synthesis from pentaerythritol, and was shown to form strong complexes with potassium ions in deuteriochloro-form-carbon disulphide solution. ... 

Figure 7.5 Synthesis of hyperbranched glyco-conjugated polymer (Poly6a and Poly6b) by ringopening multibranching polymerization of 1,4-anhydroerythiitol (6a) and 1,4-anhydro-L-threitol (6b) using trifluoromethanesulfonic acid (CF3SO3H) or fluorosulfonic acid (FSO3H).

Figure 7.8 Synthesis of hyperbranched polytetritol (PolylOa and PolylOb) by ring-opening multibranching polymerization of 2,3-anhydroerythritol (10a) and 2,3-anhydro-DL-threitol (10b), respectively.

Imai, T., Satoh, T., Kaga, H. et al. (2004) Synthesis of hyperbranched carbohydrate polymer by ring-opening multibranching polymerization of 1,4-anhydroerythritol and 1,4-anhydro-L-threitol. Macromolecules, 37,3113-3119. 

Imai, T., Nawa, Y., Kitajyo, Y. et al. (2005) Synthesis of hyperbranched polytetritol by ring-opening multibranching polymerizations of 2,3-anhydroerythritol and 2,3-anhydro-Dl-threitol. Macromolecules, 38,1648-1654. 

Anhydro-l,4-di-0-benzyl-L-threitol on reaction with allylmagnesium bromide, osmium tetroxide, sodium periodate then HCl affords methyl 3-C-(benzyloxymethyl)-2,3-dideoxy-L-r/ireo-pentofuranoside as a useful intermediate for the synthesis of 2 3 -dideoxy-3 -C-(hydroxymethyl)-4 -thionucleosides. In an alternative route to such nucleosides the intermediate branched-sugar 50 was prepared in which the hydroxymethyl group was introduced into the 3-position by a light-induced addition of methanol to 6-O-rerr-butyldimethylsilyl-D-g/yceru-pent-2-eno-1,4-lactone (see Vol. 26, p. 242, ref. 159). ... 

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