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Synthesis of 1,6‐Dideoxynojirimycin, 1,6‐Dideoxy‐ D ‐ allo ‐nojirimycin, and 1,6‐Dideoxy‐ D ‐ gulo ‐nojirimycin via Asymmetric Hetero‐ Diels‐Alder Reactions
Author(s) -
Defoin Albert,
Sarazin Hervé,
Streith Jacques
Publication year - 1996
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19960790223
Subject(s) - chemistry , hydrogenolysis , stereochemistry , derivative (finance) , ring (chemistry) , diol , catalysis , organic chemistry , financial economics , economics
Asymmetric Diels‐Alder reaction of sorbaldehyde O ‐methyloxime 1d with chiral chloronitroso derivative 2 of D ‐mannose, followed by osmylation of the primary cycloadduct, led to diol 6a with excellent enantioselectivity (ee > 99%; Scheme 1 ). Catalytic hydrogenolysis of 6a gave 1,6‐dideoxy‐ D ‐ allo ‐nojirimycin ( 7a ). Nucleophilic ring opening of cyclic sulfate 8 allowed a straightforward synthesis of 1,6‐dideoxynojirimycin ( 11 ) and of 1,6‐dideoxy‐ D ‐ gulo ‐nojirimycin ( 12 ; Scheme 2 ).