ISSN:
0947-6539
Keywords:
cleavage reactions
;
enzyme inhibitors
;
glycosides
;
rearrangements
;
transition states
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A 2-deoxyisomaltose analogue of acarbose was stereoselectively synthesised in 11 steps with a total yield of 7% starting from 2,6-dibromo-2, 6-dideoxy-D-mannono-1,4-lactone (6). The latter was reduced to the lactol, converted to the methyl glycoside (7) and hydrogenated to the methyl 6-bromo-2,6-dideoxyglycoside (8). Benzylation of the hydroxy groups, elimination of bromine to a 5-ene and Ferrier carbocyclisation gave (2S, 3R)-2,3-bisbenzyloxycyclohex-5-enone (12). 1, 2-addition of benzyloxymethyl lithium at -110°C gave a 6:1 mixture of tertiary alcohols 13; the (1S) isomer was the major one. Reaction with trichloroacetyl isocyanate gave a carbamate 19, which, when dehydrated to the cyanate, spontaneously underwent [1,3] sigmatropic rearrangement to an isocyanate, which on addition of methanol gave the methylcarbamate 20. Basic hydrolysis of this compound gave (2R, 3R,5R)-5-amino-1-benzyloxymethyl-2,3
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19970030318
Permalink
