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Glycosylidene Carbenes. Part 32
Author(s) -
Mangholz Sissi E.,
Briner Karin,
Bernet Bruno,
Vasella Andrea
Publication year - 2003
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.200390202
Subject(s) - chemistry , acylation , yield (engineering) , hydrolysis , acetylation , sulfonyl , stereochemistry , acetyl chloride , medicinal chemistry , organic chemistry , catalysis , alkyl , biochemistry , materials science , gene , metallurgy
Acylation and sulfonylation of the N , N ′ ‐ unsubstituted glucosylidenespirodiaziridines 1A / 1B 95 : 5 with Ac 2 O, BzCl, FmocCl, TsCl, (naphthalen‐2‐yl)sulfonyl, and (2,4,6‐triisopropylphenyl)sulfonyl chloride, and concomitant rearrangement gave the acylated and sulfonylated gluconolactone hydrazones 2B – 2G in 40–83% yield ( Scheme 2 ). Similarly, the galacto and manno analogues 3A / 3B 95 : 5 and 5A / 5B 55 : 45 and the mannofuransoylidene‐diaziridine 30 were acetylated and tosylated to give 4A, 4B, 6, 31A , and 31B (55–73% yield; Schemes 2 and 5 ). 15 N‐Labelling of 11A / 11B and 14A / 14B showed that the pseudoequatorial NH of the gluco diaziridines 1 and the pseudoaxial NH of the galacto diaziridines 3 were preferentially acetylated and tosylated ( Scheme 3 ). Sulfonylation of the N ‐methylated diaziridines 19A / 19B 72 : 28, 22A / 22B 85 : 15, 25A / 25B 85 : 15, 28A / 28B 80 : 20, and 33A / 33B / 33C / 33D 76 : 4 : 12 : 8 yielded the N ‐methyl‐ N ‐tosylglyconolactone hydrazones 20, 23, 26, 29 , and 34 (44–66%; Schemes 4 and 5 ). The methylated N‐atom of the diaziridines proved more reactive, irrespective of the configuration at C(2) and C(4). The products were readily hydrolysed to glyconolactones.