Glucitol 6-tosylate

In the course of the synthesis173 of oxaprostaglandins from 1,4 3,6-dian-hydro-D-glucitol, the latter was first monotosylated at the 5-position and the ester benzylated, to afford 82. Elimination of the tosyl oxy group under special conditions yields the enolethers 83 and 84 (see Scheme 16) as a 2 1 mixture which can be separated by column chromatography. 

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... 

The extension of the reaction with sodium iodide to tosyl derivatives of other acetals of iditol, glucitol, and mannitol could provide evidence for the conformation of 2,4 3,5-diacetals of mannitol and, more important, lead to a clarification of the steric requirements of this reaction. The importance of 2,4 3,5-diacetals of talitol, at present unknown, is now clear they will have one axial and one equatorial terminal group (see LIU), and the trans ring junction imposes a rigidity of conformation greater than that of any of the diacetals with cis junctions. 

Rules (1) and (3) are extensions of the arguments used by Matheson and Angyal " to explain the behavior of the di-O-tosyl derivatives of the three dianhydrides toward sodium iodide. These authors found that, in the d-mannitol derivative, both tosyloxy groups are readily replaceable by iodine but in the D-glucitol derivative only one, and in the L-iditol derivative neither, tosyloxy group was replaceable. Wiggins and Wood had obtained a parallel series of results from reactions of the di-O-tosyl and di-O-mesyl... 

Tosyl l,5-Anhydro-6-0-tosyl-D-glucitol C13H18O7S 318.347 Syrup. [a]g -i-52 (c, 1.6 in CHCI3). 6-Tosyl, tri-Ac 2,3,4-Tri-0-acetyl-l,5-anhydro-6-O-tosyl-D-glucitol C19H24O10S 444.459 Mp 144-145°. Mg -1-63 (c, 1.2 in CHCI3). 

Tosyl 2,5 3,6-Dianhydro-I-deoxy-4-0-tosyl-D-glucitol C13H16O5S 284.332 Cryst. (Et20/petrol). Mp 83-85°. Mg° +62 (c, 1 in CHCI3). 

Di-O-isopropylidene-l -O-tosyl-D-glucitol. 1,2 3,4-Di-O-isopropylidene-6-O-tosyl-L-gulitol [104527-46-0]... 

Acetyl-l,4 3,6-dianhydro-D-glucitol, D-503 5-0-Acetyl-l,4 3,6-dianhydro-D-glucitol, D-503 4-0-Acetyl-l,6 2,3-dianhydro-p-D-gulopyranose, D-505 4-0-Acetyl-l,3 2,5-dianhydro-6-0-tosyl-L-iditol, D-506... 

Dianhydro-l-deoxy-4-0-mesyl-D-glucitol, D-492 2,5 3,6-Dianhydro-l-deoxy-4-0-tosyl-D-glucitol, D-492 1,2 3,4-Di-0 -benzylidene-5-deoxy-D-arabinitol, D-40 l,2-Dideoxy-am6mo-hexitol Y>-form, D-595 i>-erythro iorm, T-176 moM K) 2-Heptulose D-form 1-Deoxy, H-62 Methyl l-deoxy-D-r/6o-2-hexulopyranoside, D-222... 

Diamino-1,6-dideoxy-2,3,4,5-tetra-0 -methyl-i>mannit ol, D-448 2,3 4,5-Dianhydroallitol, D- 2 2,5 3,4-Dianhydroaltritol D-form, D-489 2,5 3,4-Dianhydroaltritol L-form, D-489 2,5 3,4-Dianhydroaltritol DL-/orm, D-489 l,2 4,5-Dianhydro-3-0-benzoylxylitol, D-516 l,4 3,6-Dianhydro-5-0-benzyl-D-glucitol, D-503 2,5 3,6-Dianhydro-l-deoxyglucitol D-form, D-492 2,5 3,6-Dianhydro-l-deoxy-4-0-mesyl-D-glucitol, D-492 2,5 3,6-Dianhydro-l-deoxy-4-0-tosyl-D-glucitol, D-492 2,5 3,4-Dianhydro-l,6-di-0-benzoyl-D-altritol, D-489 l,4 3,6-Dianhydro-2,5-di-0-benzoyl-D-iditol, D-507 l,4 3,6-Dianhydro-2,5-di-0-benzoyl-L-iditol, D-507 l,4 3,6-Dianhydro-2,5-di-0-benzoyl-DL-iditol, D-507 2,3 4,5-Dianhydro-l,6-di-0-benzoyl-D-iditol, D-662... 

Di-0 -isopropylidene-D-glucitol, G-247 2,3 5,6-Di-0-isopropylidene-D-glucitol, G-247 3,4 5,6-Di-0-isopropylidene-D-glucitol, G-247 3,4 5,6-Di-0-isopropylidene-D-arai>iMO-hexitol, D-183 1,2 3,4-Di-0 -isopropylidene-D-mannitol, M-25 1,2 3,6-Di-0 -isopropylidene-D-mannitol, M-25 1,2 4,5-Di-0 -isopropylidene-D-mannitol, M-25 1,2 4,6-Di-0 -isopropylidene-D-mannitol, M-25 1,2 5,6-Di-0 -isopropylidene-D-mannitol, M-25 2,3 4,5-Di-0 -isopropylidene-D-mannitol, M-25 2,4 3,5-Di-0 -isopropylidene-D-mannitol, M-25 1,2 5,6-Di-0 isopropylidene-L-mannitol, M-25 3,4 5,6-Di-0-isopropylidene-L-rhamnitol, R-7 l,2 5,6-Di-0-isopropylidene-D-talitol, T-3 3,4 5,6-Di-0-isopropylidene-l-0-tosyl-D-glucitol, G-247 3,4 5,6-Di-0-isopropylidene-2-0-tosyl-D-glucitol, G-247 3,4 5,6-Di-0-isopropylidene-2-0-tosyl-L-rhamnitol, R-7 1,3 4,6-Di-0 -methylenegalactitol, G-4 2,3 4,5-Di-0-methylene-D-mannitol, M-25 l,3 4,6-Di-0-methylene-D-talitol, T-3 2,3 4,5-Di-0-methylene-D-talitol, T-3 2,5 4,6-Di-O-methylene-3-0-tosyl-L-rhamnitol, R-7 N-(3,4-Dimethylphenyl)-L-ribitylamine, A-326... 

An attempt to synthesize 2,4-0-benzylldene-l-0 -tosyl-D-glucitol by monitored hydrolysis of epoxide (28) led instead to products... 

The 1-thio-D-glucitol derivative (9) has been obtained in three steps from 2,3,4,6-tetra-Q-benzyl-D-glucose by way of the tosylate (8). Mono- and di-sulphide bridged dimers (10) and (11)... 

Carbohydrate derivatives. A soln. of Na in dry methanol added at 0 to a stirred soln. of 6-acetylthio-6-deoxy-l,3 2,4-di-0-ethylidene-5-0-tosyl-D-glucitol in chloroform, and vigorously stirred for 10 min. 5,6-dideoxy-5,6-epithio-l,3 2,4-di-0-ethylidene-L-iditol (Y 89%) dissolved in a soln. of KOH and GSg in methanol, and refluxed 2 hrs. 5,6-dideoxy-l,3 2,4-di-0-ethylidene-5,6-thio-carbonyldithio-L-iditol (Y 93%) in tetrahydrofuran added dropwise during ca. 30 min. to a stirred slurry of LiAlH4 in anhydrous ether at such a rate that the yellow color is continuously discharged 5,6-dideoxy-l,3 2,4-di-0-ethylidene-5,6-dimercapto-L-iditol (Y 88%).— The epithio compounds are a new type of carbohydrate derivative. The reductive fission of cyclic trithiocarbonates provides a useful method for the prepn. of dithiols, e.g. vicinal disec. dithiols which may not be readily accessible by other routes. F. e. s. L. N. Owen, A. M. Greigh-ton, and S. M. Iqbal, Soc. 1960, 1024, 1030. 

The dihydrofuran derivative 143 has been prepared ultimately from glucitol via the dianhydride ditosylate 139. Reaction with sodium iodide in acetone gave a mixture of mono- and diiodides 140, 141, which were collectively converted to tosylate 142 and hence 143 on reaction with methyllithium (Scheme 30). ... 

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