5 -deoxy-4 -fluoro-5 -iodo-, preparation

Deoxy-4-fluoro-D-glucopyranosyl thymine and 2-deoxy-2-fluoro-D-arabino-furanosyl derivatives of 5-substituted-cytosine and -uracil have been prepared by standard methods from the corresponding fluoro-sugar the uracil derivatives stopped replication of Herpes simplex virus (HSV-1) in vitro. 5-Deoxy-5-iodo-adenosine derivatives have also been prepared from iodo sugars. ... 

Selective acid>catalysed methanolysis of 2,3,2, 3 -tetra-0-benzyl-4,6 4, 6 -di-0-benzylidene-a,a-trehalose gave the monoacetal which was converted into the dimesylate and from this 6-deoxy-6-fluoro-a,a-trehalose was obtained. In the course of the work 4-chloro-4,6-dideoxy-6-fluoro-a-D-galactopyranosyl a-D-glucopyranoside was produced (as a derivative), and 6-iodo, 6,6 -di-iodo, 6-azido-, and 6,6 -diazido-trehalose compounds were also prepared. 6-Deoxy-6-fluoro- and 6-deoxy-6-iodo-trehalose were also obtained by way of the... 

D-lyxopyranosyl nucleosides with hydrogen halides to give the 3 -bromo- or 3 -chloro-3 -deoxy-nucleosides (406), or a mixture of the 2 - and 3 -fluoro-deoxy-nucleosides (407). 9-(3-Deoxy-3-iodo-)3-D-xylofuranosyl)hypoxanthine has been synthesized and converted into 3 -amino-3 -deoxy- and 3, 4 -unsatu-rated nucleosides as shown in Scheme 138. Both l-(2-deoxy-2-fluoro- and 2-chloro-2-deoxy-j8-D-arabinofuranosyl)cytidine have been prepared from the corresponding halogeno-sugar derivatives by standard methods (see Schemes 43 and 46). ... 

Many 5-alkyl-, 5-alkenyl-, and 5-alkynyl-l-(2-deoxy-2-fluoro- 5-D-arabin-ofuranosyl)pyrimidines (750 - 752 and 765 - 767) were prepared - " by condensation of 742 (or the equivalent, such as 743) with C-5-substituted pyrimidine derivatives, or by attachment of a C-fragment to C-5 of the existing nucleosides through their 5-iodo or 5-chloromercuri derivatives, or by further conversion of the attached C-5 substituent into another one. ... 

The synthesis of a series of 2 -fluoro-5-substituted arabinofuran-osyl-cytosines and -uracils has been described. 5-Methyluracil and 5-iodocytosine derivatives were the most effective against herpes simplex virus. The arabino configuration was essential for antibiotic activity, and corresponding chloro and bromo analogues were less effective.5 -Bromo-, 5 -fluoro-, and 5 -iodo-deriv-atives of 5-fluorouracil have been prepared conventionally. The a-anomer of 5 -fluoro-5 -deoxyuridine has been synthesized from a 1,2-oxazoline derivative of 5-deoxy-5-fluoro-D-ribose, in turn prepared by a sulphonate displacement using pyridinium fluoride. Treatment of 1-(o-D-arabinofuranosyl)-uracil with diphenylcarbonate yielded the 1,4-oxazin derivative (23) which yielded the 2 -chloro-2 -deoxy-arabino-a-nucleoside (24) on chlorination this was then reduced to the 2 -deoxy analogue (25). 5-Fluorouridine has been... 

The 2-deoxy-2-fluoro-2-iodo-hexopyranoses 1 and 2 have been prepared from 2-fluoro-D-glucal (Scheme 1). Haloetherification of glycal 3 (NBS, ROH) gave the P-glycosides 4, which underwent radical cyclisation on abstraction of the bromine atom (see Chapter 14). Free radical bromination (NBS, CCI4, hv) of... 

The anticancer nucleoside Gemcitabine as its monophosphate derivative (3) has been modified by conjugation of squalene at the N4-position. Using a combination of cryo-EM and SAXS it was shown that the squalenoyl derivative exists as a unilamellar liposome, and that the nanoassembly exhibited enhanced activity compared with Gemcitabine in a resistant cell line." Various C6-modified 2 -deoxy-2 -fluoro-dUMP derivatives have been prepared as potential inhibitors of orotidine 5 -monophosphate decarboxylase (ODCase) of these, the most potent analogue was the 6-iodo-derivative which was found to covalently inhibit ODCase. Aminoacyl-tRNAs... 

---