3- Deoxy-3-fluoro-sucrose

Stoichiometric quantities of uridine diphosphate glucose were used, in the presence of a transfer enzyme, sucrose synthetase, in the soluble state (extraction given). Coupling with modified D-fructose gave sucroses modified on the D-fructosyl group, on the 1 -3-mmol scale. Thus were prepared l -deoxy-l -fluoro- (59%),98 4 -deoxy-4 -fluoro- (16%), and l -azido-l -deoxy-sucrose (15%).71 6-Deoxy-6-fluoro-D-glucose was isomerized to 6-deoxy-6-fluoro-D-fructose with isomerase, and gave 6 -deoxy-6 -fluoro-sucrose.71... 

Deoxy-4-fluoro- a/flc/o-sucrose (617 4-deoxy-4-fluoro-a-D-galacto-pyranosyl D-fructofuranoside), 2,3,1, 3, 4, 6 -hexa-0-benzyl-4,6-dideoxy-4,6-difluorosucrose (618), 2,3,1, 3, 4, 6 -hexa-0-benzyl-6-deoxy-6-... 

Fig. 2.2.S.4 Sucrose analogues synthesized with recombinant SuSyl from yeast. 23 I -deoxy-l -fluoro-P-D-fructofuranosyl-a-D-glucopyranoside 24 [ C,]-ji-D-fructofuranosyl-a-D-glucopyranoside 25 a-D-glucopyranosyl-a-L-sorbofuranoside 26 a-D-glucopyranosyl-a-D-lyxopyranoside 27 2-acetamido-2-deoxy-a-D-glucopyranosyl-P-D-fructofuranoside.

Sucrose synthetase. The fructose derivatives 1-azido-l-deoxy-, 1-fluoro-l-deoxy-, 6-deoxy-, 6-fluoro-6-deoxy-, and 4-fluoro-4-deoxy-fructose have been used as glycosyl acceptors in the sucrose synthetase-catalyzed synthesis of sucrose analogs12031. 6-Deoxy- and 6-fluoro-6-deoxy-fructose were generated in situ from the corresponding glucose derivatives under catalysis by glucose isomerase[2031. Sucrose synthetase has also been extensively employed in the synthesis of nucleotide sugars[2041. 

The syntheses of sucrose 6 -phosphate, methyl a-mannopyranoside 4- and 6-phosphates, and 3-deoxy-3-fluoro-D-glucose 1- and 6-phosphates [ (57) and (58) ] have been described. Neither (57) nor (58) was a substrate for UDPGlc-pyrophosphorylase or phosphoglucomutase, although (58) was a poor substrate for glucose 6-phosphate dehydrogenase. ... 

The n.m.r. data for 6-deoxy-6-fluoro-ot- and - D-glucopyranose obtained at 300 MHz in DjO has been reported with a discussion of chemical shifts and coupling constant values. N.m.r. data on the unsaturated sugar derivatives (5) and (6), as well as on some fructofuranose derivatives useful as intermediates in a new synthesis of sucrose, have been published. The complete elucidation of the H n.m.r. spectra of the 2,3-unsaturated glycosyl phosphonates of type (7)... 

Deoxy-6-fluorosucrose and hexabenzyl-6-deoxy-6-fluoro-galacto-sucrose have been prepared by conventional steps from 1, 2,2, 3 3 6 hexa-0-benzyl-4,6-0-isopropylidene-8ucrose. The mesylate displacement by tetra-n-butylammonium fluoride used in this synthesis... 

Halogen-. Nitrogen-. Sulphur- and Seleno-containinq Compounds.-1,3,4,6-Tetra-Q-acetyl-2-deoxy-2-fluoro-/8-D-galactopyranose,the tricyclic fluoride (11), 4,1, 6 -trichloro-4,l, 6 -trideoxy-galacto-sucrose.the iodo-aldulose derivative (12), 6-deoxy-6-iodo-l,2 3,4-di-Q-isopropylidene-a-D-galactopyranose,allyl 1-deoxy-l-[(l-methyl-2-benzoyIviny1)amino)-a-D-fructofuranoside, the 1,6-lactam (13), the natSiral products alexine (14) and 3,8-diepialexine (15), the 2-amino-2-deoxy-D-mannose derivative... 

Trideoxy-3,4,6-trifluoro- C-D-galactopyranosyl fluoride has been prepared from 3-deoxy-3-fluoro- c-D-glucopyranosyl fluoride using the diethylamino-sulphur trifluoride (DAST) procedure, and its stereochemistry determined by detailed multinuclear n.m.r. experiments. The DAST method has also been used to prepare 6,6 -dideoxy-6,6 -difluoro-sucrose from 2,3,4 3 4 -P nta-0-benzoyl-sucrose. The free 1 -hydroxy group was not substituted by fluorine. 

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