Asymmetric Reaction of Simple Nitro Compounds with Chiral 1,3-Oxazolidin-2-ones

✍ Scribed by Iwona Kudyba; Jerzy Raczko; Janusz Jurczak

• Book ID: 102258310
• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: German
• Weight: 310 KB
• Volume: 87
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200490156

✦ Synopsis

Dedicated to Dr. G¸nther Ohloff on the occasion of his 80th birthday

The chiral oxazolidinone 1 ( (3aS,6R,7aR)-tetrahydro-8,8-dimethyl-2-oxo-4H-3a,6-methano-1,3-benzoxazol-3-ylacetaldehyde) was found to react stereoselectively with simple nitro compounds in the presence of Al 2 O 3 or Bu 4 NF ¥ 3 H 2 O (TBAF) as catalysts, affording the diastereoisomeric nitro alcohols 3 ± 6 with good asymmetric induction. When Al 2 O 3 was used, the (S)-configuration at the center bearing the OH group was generated, with the relative syn-configuration for the major diastereoisomers. In the case of the nitro-aldol reaction catalyzed by TBAF, an opposite asymmetric induction was found for two nitro compounds. In contrast to 1, compound 12 ( ((4R,5S)-4-methyl-2-oxo-5-phenyl-1,3-oxazolidin-3-yl)(oxo)acetaldehyde), a derivative of Evans auxiliary, gave rise to poor asymmetric induction in Henry reactions.