Stereoselective trans- and cis-dihydroxylations of 2H-pyranyl and dihydropyridinyl heterocycles synthesized from formal [3 + 3]-cycloaddition reactions of alpha,beta-unsaturated iminium ions with 1,3-dicarbonyl equivalents.
[reaction: see text]We describe here an inherent problem in direct epoxidation of the endocyclic olefin in 2H-pyrans fused to 2-pyrones. Such difficulties led to the development of highly stereoselective trans- and cis-dihydroxylations of these olefinic systems in both 2H-pyrans and dihydropyridines fused to a 2-pyrones or a 2-cyclohexenone. Protocols for the removal of the activated allylic hydroxyl group are also reported.
Zehnder
L R
LR
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Wei
L L
LL
Hsung
R P
RP
Cole
K P
KP
McLaughlin
M J
MJ
Shen
H C
HC
Sklenicka
H M
HM
Wang
J
J
Zificsak
C A
CA
D000470:Alkaloids / Q000737:chemistry; D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D003512:Cyclohexanones / Q000737:chemistry; D006574:Heterocyclic Compounds, 2-Ring / Q000138:chemical synthesis* / Q000737:chemistry*; D006900:Hydroxylation; D007097:Imines / Q000737:chemistry; D015394:Molecular Structure; D011714:Pyrans / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D011753:Pyrones / Q000737:chemistry*; D011804:Quinolines; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D000470:Alkaloids; D000475:Alkenes; D003512:Cyclohexanones; D006574:Heterocyclic Compounds, 2-Ring; D007097:Imines; D011714:Pyrans; D011725:Pyridines; D011753:Pyrones; D011804:Quinolines; C432303:arisugacin A; C432304:arisugacin H; C432305:lepadin A; C432306:orevactaene; C036468:cyclohexanone