Hexopyranose preparation

All derivatives used were prepared by essentially standard literature procedures and had physical constants in accord with previously reported values. Furthermore, the P.M.R. spectra were in each case consistent with the assigned structures. All solutions were concentrated under reduced pressure and m.p. s are uncorrected. (I) 2-Deoxy-D-arafczno-hexopyranose was a commercial sample from Pfanstiehl Lab. Inc., Waukegan, Illinois and was used without further purification. (II) 3, 4, 6-Tri-O-acetyl-D-glucal (1) was a commercial sample from Aldrich Chem. Co., Milwaukee, Wisconsin and was purified by distillation and recrystallized three times from aqueous ethanol. (Ill) 1, 3, 4, 6-tetra-0-acetyl-2-deoxy-a-D-arahino-hexopyranose (4) was prepared by the method of Bonner (11) while the corresponding / -anomer (5) was synthesized following the procedure of Overend, Stacey, and Stanek (47). (IV) 5, 6-Dideoxy-1, 2-0-isopropylidene-a-D-xj/io-hex-5-enofuranose (20) was provided by A. Rosenthal and G. Khan of this Department. 

This process (also known as the Ferrier II Reaction ) has proved to be of considerable value for the efficient, one-step conversion of 5,6-unsaturated hexopyranose derivatives into functionalized cyclohexanones useful for the preparation of such enantiomerically pure compounds as inositols and their amino, deoxy, unsaturated and selectively O-substituted derivatives, notably phosphate esters. In addition, the products of the carbocyclization have been incorporated into many complex compounds of interest in biological and medicinal chemistry. ... 

T.-M. Cheung, D. Horton, and W. Weckerle, Preparative synthesis of 3-amino-2,3,6-trideoxy-L-/yv<9-hexopyranose derivatives, Carbohydr. Res., 74 (1979) 93-103. 

The derivative (9) of 3,6-dideoxy-a-D-xyIo-hexopyranose (abequose) was isolated from a strain of Salmonella typhimurium,16 that (10) of 3,6-dideoxy-a-D-nfco-hexopyranose (paratose) from Salmonella paratyphi,54 and a mixture of 10 and the ester (11) of 3,6-dideoxy-a-D-arabino-hexopyranose (tyvelose) from Salmonella enteritidis.,6 It was shown that these derivatives are formed from cytidine 5 -(a-D-glu-copyranosyl pyrophosphate) by treatment with nicotinamide adenine dinucleotide (NAD+) and reduced nicotinamide adenine dinucleotide phosphate (NADPH) in the presence of cell extracts of the respective bacterial strain. For example, formation of 9 is characteristic of preparations from Salmonella, group B,55,56 or Pasteurella pseudotuberculosis, type II.56 The derivative 10 was obtained with extracts of Salmonella, group A,56 and Pasteurella pseudotuberculosis, type I and III,56 and a mixture of 10 and 11 with those of Salmonella, group D,55-60 or Pasteurella pseudotuberculosis, type IV 56.59,60 Under similar conditions, the ester (12) of cytidine 5 -pyro-... 

When either of the two methods in the previous Subsection is employed in order to introduce a phosphino (or phosphinyl) group at C-5 of 5-deoxy-D-xyZo-hexofuranoses, only 5-deoxy-5-phosphino- (or -5-phos-phinyl)- L-idopyranoses are produced for instance, 50 — 60 (and 64) — 63 (and 65), and 73 — 78 — 85 — 88 — 90. Therefore, in order to prepare hexopyranoses of the D-gluco type having phosphorus in the hemiacetal ring, an alternative approach had to be devised. 

For the preparation of a 3 -deoxy Lex analogue, an acylated 3-deoxy-D-. v/o-hexopyranose was used. The latter was prepared either from phenyl 1-thio-D-galactopyranoside78 or from l,2 5,6-di-0-isopropylidene-a-D-galactofuranose,79 via the Barton and McCombie deoxygenation method. 

A convenient approach for the preparation of 3-deoxy-D-xy/o-hexopyranose (27) starts from 1,2 5,6-di-(9-isopropylidene-ot-D-glucofuranose and proceeds via the 3,4-unsaturated derivative 28 (Scheme 15).80... 

The thioglycoside derivative of 4,6-dideoxy-i-/vA o-hexopyranose 160, useful as glycosyl donor has been prepared starting from the ethyl 1-thio-a-L-rhamnopyranoside (159, Scheme 46). 

Four corresponding deoxy derivatives have also been prepared 1,6 2,3-dianhydro-4-deoxy-jS-D-/yxo-,432,433 and -D-rZZw-hexopyranose,169,432 and l,6 3,4-dianhydro-2-deoxy-/l-D-/vA o-, and -D-r[Pg.157]

In the case of 1,6 2,3- (136) and l,6 3,4-dianhydro-/I-D-talopyranoses, the diaxial opening of the oxirane ring prevails, but a trend to diequatorial opening496 498 is apparent with l,6 2,3-dianhydro-4-deoxy- and 1,6 3,4-dianhydro-2-deoxy-/l-D-/yxo-hexopyranoses.169,432,493 Using 1,6 2,3- and l,6 3,4-dianhydrohexopyranoses as starting compounds allowed the preparation of a complete series of 12 isomeric 1,6-anhydro-monodeoxy-/Fn-hexopyranoses and 6 corresponding 1,6-anhydro-dideoxyhexoses,499 mainly by catalytic or complex hydride reductions.462,500... 

E. Wu and Q. Wu, Preparation of hexopyranose 2-tosylates and their facile conversion into 1,2-anhydrohexopyranoses by internal displacement, Carbohydr. Res., 250 (1993) 327-333. 

D. Lafont, P. Boullanger, O. Cadas, and G. Descotes, A mild procedure for preparation of 1,6-anhydro-jS-D-hexopyranoses and derivatives, Synthesis, (1989) 191-194. 

I. Cerny, M. Budesinsky, T. Trnka, and M. Cerny, Preparation of 2-amino- 1,6-anhydro-2,3-dideoxy-jS-D-arabino-hexopyranose. H- and 13C-N.M.R. spectra of deoxy derivatives of 2-amino-l,6-anhydro-2-deoxy-D-glucose and 2-amino-l,6-anhydro-2-deoxy-D-mannose, Carbohydr. Res., 130 (1984) 103-114. 

J. Kroutil, T. Trnka, M. Budesinsky, and M. Cerny, Preparation of 2,3-dideoxy-2,3-epimino and 3,4-dideoxy-3,4-epimino derivatives of l,6-anhydro-/8-D-hexopyranoses by Mitsunobu reaction, Collect. Czech. Chem. Commun., 63 (1998) 813-825. 

T. Trnka, M. Budesinsky, and M. Cerny, Improved preparation of l,6-anhydro-4-deoxy-2-O-p-toluenesulphonyl-jS-D-xy/o-hexopyranose and of its D-[4-2H]g/uco-analogue from l,6 3,4-dianliydro-2-0-p-toluenesulphonyl-/ -i)-galactopyranosc, Carbohydr. Res., 259... 

IV) (l,6-anhydro-/8-D-glucopyranose).7 Subsequent studies have elucidated the interesting steric factors which control the reaction,4 8 and the transformation has been applied in a useful laboratory procedure for the preparation of l,6-anhydro-/3-D-hexopyranoses.8-910... 

As summarized in Scheme 37, gulo- and allo-configured l-amino-5a-carba-P-D-hexopyranoses 228 and 231, as well as the related amino acid counterparts, 229 and 232, sprang from the common lactam intermediate 224. The preparation of aldehyde 224 from silyloxypyrrole 76 and D-glyceraldehyde 11 entailed a Lewis acid promoted vinylogous cross aldolization followed by functional group manipulation, including olefin... 

In an examination of the stereochemical course of addition of phosphorodithioic acids to 1,2-unsaturated pento- and hexopyranoses, S-deuterated 0,0-dimethyl- and 0,0-bis(2,2-dimethyl-propyl) phosphorodithioates were prepared and reacted with D-glucal. These reactions were found to be fully stereoselective at both reaction centers C-l and C-2 and afforded S-D-ara-binopyranosyl phosphorodithioates 8 and 9 in quantitative yield deuterated at C-2 of the pyranosyl ring14. s... 

Pratt, J W, Richtmyer, N K, Crystalline 3-deoxy-a-D-nho-hexose. Preparation and properties of 1,6-anhydro-3-deoxy-a-D-arafa>io-hexopyranose, 1,6-anhydro-3-deoxy-p-D-n ho-hexopyranose and related compounds, J. Am. Chem. Soc., 79, 2597-2600, 1957. 

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