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The Ring Expansions of Glyceraldehyde‐Derived Aziridine‐2‐carboxylates to Oxazolines Take Place with an Uncommon Regiochemistry
Author(s) -
Cardillo Giuliana,
Gentilucci Luca,
Mohr Galla Pericot
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200109)2001:18<3545::aid-ejoc3545>3.0.co;2-k
Subject(s) - regioselectivity , chemistry , aziridine , oxazoline , ring (chemistry) , carboxylate , stereoselectivity , hydrolysis , stereochemistry , derivative (finance) , medicinal chemistry , organic chemistry , catalysis , financial economics , economics
The ring expansion of the D ‐glyceraldehyde‐derived ethyl trans ‐ N ‐benzoylaziridine‐2‐carboxylate 9 occurs with retention of configuration, giving the ethyl trans ‐oxazoline‐5‐carboxylate 10 as the only product. The observed regioselectivity is rather unusual, since aziridine‐2‐carboxylates generally rearrange to give oxazoline‐4‐carboxylates. Conversely, the ring expansion of the cis ‐ N ‐benzoyl compound 11 under the same reaction conditions is much slower and less stereoselective, giving a mixture of cis ‐ and trans ‐oxazolines, but with the same regioselectivity. The hydrolysis of 10 under mild conditions permits the synthesis of the 3‐amino‐3‐deoxy‐ D ‐xylonic acid derivative 13 .