A methyl 2-deoxy

Deoxy-D-arafnno-hexose (55) was treated in methanol with hydrogen chloride according to a procedure79 which was purported to yield almost exclusively a mixture of the anomers of methyl 2-deoxy-D-arabino-hexofur anoside. It has now been shown78 that the latter consists, in fact, of an anomerically pure methyl 2-deoxy-D-arabino-hexofuranoside (77), plus substantial proportions of an approximately 1 1 mixture of methyl 2-deoxy-a- and jS-D-orabmo-hexopyranosides (78) and (79), and unreacted 2-deoxy-D-arabino-hexose (55). p-Nitrobenzoylation of the sirupy, quadripartite mixture led to a mixture of p-nitrobenzoic esters from which, by fractional recrystallization, there was obtained in pure form a methyl 2-deoxy-3,5,6-tri-O-p-nitrobenzoyl-D-arabino-hexoside (80). Attempts to replace, directly, the severely hindered methoxyl group at C-l of (80) by halide failed. 

Reductive detosyloxygenation (NaBHi -DMS0) was a key step in the conversion of a methyl 2-deoxy-4-0-tosyl-a-D-rlbo-hexopyranoside derivative into the 2,4,6-trldeoxy-6-iodo-derivative (17), required as a chiral intermediate for the synthesis of certain natural enzyme inhibitors related to mevlnolin (see also Chapter 23)... 

Deoxy-D-galactose 3-phosphate was prepared from 4,6-benzylidene a-methyl-2-deoxy-D-gaiactoside and diphenyl phosphorochloridate . ... 

Deoxy-D-galactose 6-phosphate was prepared by phosphorylation of 3,4-isopropylidene a-methyl-2-deoxy-D-galactoside . ... 

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