D-Glucitol 1.5- anhydro

Sugihara and Schmidt49 reported the isolation of 2,5-anhydro-D-glucitol in crystalline form its preparation on a relatively large scale has been described in the patent literature,50 and consists in the thermal dehydration of D-mannitol. The process leads to the formation of 1,4-anhydro-D-mannitol, 1,5-anhydro-D-mannitol, 1,4 3,6-dianhydro-D-mannitol, and 2,5-anhydro-D-glucitol, which is isolated as the crystalline 1,3-O-isopropyIidene derivative (35). 

The competitive inhibition of aldolase by a number of structural analogs of D-ftuctose 1,6-diphosphate has been investigated.120 Among these analogs were 1,4-anhydro-DL-ribitol 5-phosphate, 1,4-anhydro-DL-xylitol 5-phosphate, 1,4-anhydro-D-arabinitol 5-phosphate, 2,5-anhydro-D-mannitol 1,6-diphosphate, and 2,5-anhydro-D-glucitol 1,6-diphosphate. Their respective, enzyme-inhibitor,... 

Regtosdective reduction of an epoxide. A key step in a short synthesis of (+)-muscarine (6) from the dibenzoate of 2,5-anhydro-D-glucitol (1) involves reduction of the epoxide 2. Use of SMEAH gives a 12 1 mixture of 3 and 4 use or LiAlH4 gives the same diols in the ratio 3 1. ... 

Nevertheless, compound 81 was definitely obtained later by deamination of 2-amino-l,6-anhydro-2-deoxy-j6-D-mannopyranose (103) with nitrous acid, and was identified by reduction to 2,5-anhydro-D-glucitol.366 An analogous deamination was performed with 2-amino-l,6-anhydro-2-deoxy-3-0-tosyl-/l-D-altropyranose to give, after detosylation, 2,5-anhydro-D-allose.361... 

Both 2,5-anhydro-D-mannitol and 2,5-anhydro-D-glucitol contain the requisite 1,4-anhydro-D-arabinitol ring system.215-240 The D-mannitol derivative is about 3.5 times as potent an inhibitor as the D-glucitol derivative, perhaps by virtue of the fact that it may bind to con A either through the hydroxyl groups at C-l, C-3, and C-4, or C-3, C-4, and C-6 (compare Ref. 429). Finally, the important observation that methyl a-and /3-D-fructofuranoside are inhibitors (the (3 anomer being approximately three times as active as the a anomer) provides an explanation for the interaction of con A with plant and bacterial levans120-215-364 (see Section II,l,h). 

A double-headed example, 2,5-anhydro-l,6-bis(4-amino-5-aminocar-bonyltriazol-3-yl)-l,6-dideoxy-3,4-di-0-methyl-D-glucitol (55), was similarly prepared from 1,6-diazido-1,6-dideoxy-3,4-di-0-methyl-2,5-anhydro-D-glucitol (25°C, 15 hr, 49%). [Note glucitol (sorbitol) is a hexitol] (83 ACH443). 

Anhydro-alditols - The preparations of polyesters based on l,4 3,6-di-anhydro-D-glucitol and -o-mannitol with succinyl-, glutaryl- and adipoyl-dichlor-ides have been reported. Also reported have been the syntheses of poly(1 6)-2,5-anhydro-D-glucitol and its 3,4-di-0-alkylated derivatives by Lewis acid induced polymerization of 3,4-di-0-alkyl-l,2 5,6-dianhydro-D-mannitol base induced polymerization of l,2 5,6-dianhydro-3,4-di-0-methyl- or 3,4-di-O-iso-propylidene-D-mannitol base induced polymerization of l,2 5,6-dianhydro-3,4-di-O-pentyl- or di-O-decyl-o-mannitol and base induced polymerization of l,2 5,6-dianhydro-3,4-di-0-methyl-L-iditol. The solubilities of these 3,4-di-O-alkylated and deprotected polymers in aqueous and organic media were studied. Further, it has been reported that 2,5-anhydro-3,4-di-0-methyl-D-glucitol linked 1,6 to silica gel was useful for the optical resolution of amines and amino acid salts. ... 

Anhydro-D-glucitol, 2,5-anhydro-D-mannitol and their 6-phosphate and... 

Muscarine (1) has been produced from the 2,5-anhydro-D-glucitol compound (2) by methods outlined in Scheme 1, and the four stereoisomers of the spiro-compound (3) were synthesized by way of dithiane derivatives such as (4),... 

Another study pertinent to the present discussion is that of the acid-catalyzed dehydration of tetratols, pentitols, and hexitols, all of which yield tetrahydrofuran derivatives as the primary products. These reactions are first order with respect to the alcohol and the acidity function Hq, and the direct relationship shown from plots of versus Hq implies that the reaction proceeds via a protonated intermediate.In all cases except one, the major cyclic product is derived from HO-5 displacement of water from C-1. The exception is D-mannitol (213), where HO-3 participation leads to a slight preference for formation of 2,5-anhydro-D-glucitol (214) over 1,4-anhydro-D-mannitol (215). Inversion at C-2 occurs with HO-5 participation during ring opening of the epoxide (214). 

D-Mannitol 1.4- Anhydro-D-mannitol (41 %) 2.5- Anhydro-D-glucitol (45 %,) 1.5- Anhydro-D-mannitol (14%) 13... 

It is not known if m-tyrosine can be converted to l-DOPA by a cell-free extract of a species susceptible to m-tyrosine. If so, would the process be highly efficient in vivol Synthetic proherbicides, such as diclofop-methyl [11], that are inactive at the molecular target site are much more effective when applied to intact plants than the active molecule to which they are converted in vivo. This is due to superior cuticular and cellular uptake of the proherbicide. Some potent natural phytotoxins from microbial origin, such as hydantocidin and 2,5-anhydro-D-glucitol, are protoxins [170-171]. 

Dayan, F.E. et al. (2002) Bioactivation of the fungal phytotoxin 2,5-anhydro-D-glucitol by glycolytic enzymes is an essential component... 

Hyperbranched Poly(2,5-anhydro-D-glucitol) by Polymerization of ly2 5y6-Dianhydro-D-mannitol... 

Figure 7.10 Synthesis of hyperbranched poly(2,5-anhydro-D-glucitol) (Poly 13) by cationic cyclopo-lymerization of l,2 5,6-dianhydro-D-mannitol (13).

Although the anionic polymerization of 13 tended to form gels, the cationic polymerization proceeded through a proton-transfer reaction mechanism to produce hyperbranched glyco-conjugated polymer Poly 13 mainly consisting of 2,5-anhydro-D-glucitol units. This was the first report of the synthesis of a hyperbranched polymer via a cyclopolymerization mechanism. 

Umeda, S., Satoh, T., Sait(, K. et al. (1998) Synthesis of (1 6)-2,5-anhydro-D-glucitol through cycl( lymeriza-tion of 3,4-di-0-allyl-l,2 5,6-dianhydro-D-mannitol and ( tical resolution ability of its derivative in HPLC. Journal of Polymer Science, Part A Polymer Chemistry, 36,901—909. 

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