Nojirimycin 1- deoxynojirimycin

Deoxynojirimycin (DNJ, 1) was originally prepared by catalytic hydrogenation of nojirimycin, which was discovered as the first glucose-mimicking antibiotic produced by Streptomyces spp., with a platinum catalyst or by chemical reduction with NaBH4 [5,6]. Later it was isolated from the root bark of mulberry trees and called moranoline [7]. DNJ is also produced by many strains in the genera Bacillus and Streptomyces [8,9]. 

Figure 1. Diagram illustrating the common nomenclature for polyhydroxylated piperidine alkaloids, (a) 5-Amino-5-deoxy-D-glucopyranose has the trivial name nojirimycin, (b) 1-deoxynojirimycin (DNJ) is the trivial name for l,5-dideoxy-l,5-imino-D-glucitol and similarly (c) 1-deoxymannojirimycin (DMJ) is the common name for l,5-dideoxy-l,5-imino-D-mannitol.

The readily available 2,3,4,6-fefra-O-benzyl-D-glucopyranose (11) can be used for the synthesis of both nojirimycin (1) and 1-deoxynojirimycin (2) (Schemed).It was treated with EtSH to furnish 12, which was oxidized to the corresponding ketone 13 using TPAP, while the Swern oxidation method failed to produce 13. Treatment of 13 with mercury(ll) salts in the presence of methanol followed by treatment with hydroxylamine hydrochloride in the presence of pyridine afforded the oxime 14 in 73% yield. Treatment of 14 with LiAlH4 in diethyl ether followed by N-protection of the resulting diastereomeric mixture of amines with di-rert-butyl dicarbonate furnished 15 and 16 in 65 and 15% yield, respectively. Pearlman s catalytic hydrogenation of 15 over palladium hydroxide in ethanol followed by treatment of the resulting tetrol with SO2 in water furnished the sulfonic acid 17 in 80% yield. Conversion of 17 into 1 was accomplished by treatment with Dowex 1X2 (OH ) resin. 

Synthesis from i-threose Nojirimycin (1) and 1-deoxynojirimycin (2) have been synthesized from 4-6 -( err-butyldimethylsilyl)-2,3-0-isopropylidene-L-threose (118) (Scheme 22) Compound 118 was treated with trimethyl phosphonoacetate to provide the E ester 119, as a single isomer in 95% yield. Reduction of the ester group in 119 followed by Sharpless asymmetric epoxidation of the resulting allylic alcohol afforded the syn-epoxide 120. Treatment of 120 with NaNs and NH4CI in a mixture of 1,2-dimethoxyethane,... 

Bacillus (1-deoxynojirimycin), 106 Bacillus (nojirimycin), 105 Baphia racemosa [(25,3, 4, 55)-3,4,5-trihydroxypipecolic acid)], 111... 

Streptomyces lavendulae SEN-158 (1-deoxynojirimycin), 106 Streptomyces lydicus PA-5726 (galactonojirimycin), 141 Streptomyces nojiriensis sp. SF-426 (nojirimycin), 105 Streptomyces roseochromogenes (anisomycin), 46... 

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