Racemic and asymmetric Diels-Alder reactions of 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes.
Achiral and chiral 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes were prepared from readily available starting materials. Although more stable than the parent 1-amino-3-siloxy dienes, the 1-(2-oxazolidinon-3-yl)-3-siloxy-1,3-butadienes are still very reactive in Diels-Alder reactions, somewhat more than 1,3-dialkoxy-1, 3-butadienes (e.g., Danishefsky's diene). The cycloadditions of the achiral and chiral dienes with several different dienophiles were examined. The reactions proceeded in good yield, with modest to high endo selectivity. The chiral dienes exhibited excellent facial selectivity in cycloadditions with alpha-substituted acroleins, maleic anhydride and N-phenylmaleimide. Upon reduction and hydrolysis of the cycloadducts, substituted cyclohexenones were obtained with ee's ranging from 22% to >98%.
Janey
J M
JM
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, Illinois 60637, USA.
Iwama
T
T
Kozmin
S A
SA
Rawal
V H
VH
D000171:Acrolein / Q000031:analogs & derivatives / Q000737:chemistry; D002070:Butadienes / Q000138:chemical synthesis*; D003500:Cyclization; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008299:Maleic Anhydrides / Q000737:chemistry; D008301:Maleimides / Q000737:chemistry; D017646:Organosilicon Compounds / Q000138:chemical synthesis*; D013237:Stereoisomerism
D002070:Butadienes; D007202:Indicators and Reagents; D008299:Maleic Anhydrides; D008301:Maleimides; D017646:Organosilicon Compounds; D000171:Acrolein; C028525:N-phenylmaleimide