Straighforward Synthesis of a Novel Chiron and its Application to the Synthesis of (+)‐1,4‐Dideoxymannojirimycin and Further Polyoxygenated 2‐Pyperidones

Abstract

The total synthesis of (+)-1,4-dideoxymannojimycin and the enantiopure synthesis of three polyoxygenated piperidin-2ones from a novel chiron is reported. Starting from 3-deoxy-3amine-D-glucose, by means of the stereoselective aqueous SHOWO protocol (Sequential-Hydrolysis-Oxidation-Wittig Olefination), the unsaturated-7,3-lactam-D-xylofuranose derivative was prepared, which depending on the oxidative C À C bond cleavage reaction conditions for the furanose moiety, is transformed into either (+)-1,4-dideoxymannojirimycin or polyoxygenated piperidin-2-ones.The authors declare no conflict of interest.

Synthesis of a truncated tetradenolide

“…We have achieved the synthesis of the 7,3‐lactone‐xylofuranose derivative (7,3‐LXF) from diacetone d ‐glucose in grams' scale, [ 8 ] and has been applied to the synthesis of the metabolites produced by Trichoderma spp . and Penicillium isolates (Scheme 1).…”

“…In this way, we proved that the addition of the allyl group is favored on the Re face of the oxocarbenium ion (Figure 2). [ 8 ] Similarly, the hydrogenation of the CC double bonds in 9 was not selective and compound 11 was obtained (Scheme 4).…”

Ethyl (3S)-3-[(3aR,5R,6S,6aR)-6-hydroxy-2,2-dimethyltetrahydrofuro[4,5-d][1,3]dioxol-5-yl]-3-{(3S)-3-[(3aR,5R,6S,6aR)-6-hydroxy-2,2-dimethyltetrahydrofuro[4,5-d][1,3]dioxol-5-yl]-5-oxoisoxazolidin-2-yl}propanoate chloroform monosolvate

“…The Chiron known as 7,3-LXF (7,3-lactone-xylofuranose derivative; Ramírez et al, 2017), derived from d-glucose, is a versatile starting material for the synthesis of natural products, for example the metabolites produced by Trichoderma spp and Penicillium data reports isolates (Pé rez-Bautista et al, 2016). In a work aimed at the synthesis of 1-deoxynojirimycin (DNJ), an azasugar alkaloid presenting -glucosidase inhibitor properties, the title compound was obtained (Amaro Herná ndez, 2019).…”