Unexpected syn hydride migration in the non-aldol aldol reaction.
[structure: see text] Non-aldol aldol rearrangement of the epoxy silyl ether 13b afforded the expected anti methyl ketone 14, while the diastereomeric epoxy silyl ether 13a afforded the syn methyl ketone 8b via an unprecedented syn hydride migration. Calculations suggest that this unusual reaction proceeds via the carbocation, which cannot easily rotate due to steric hindrance.
Jung
Michael E
ME
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA. jung@chem.ucla.edu
van den Heuvel
Alexandra
A
Leach
Andrew G
AG
Houk
K N
KN
D000447:Aldehydes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D004986:Ether / Q000737:chemistry*; D006588:Hexanones / Q000138:chemical synthesis*; D008968:Molecular Conformation; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D000447:Aldehydes; D004852:Epoxy Compounds; D006588:Hexanones; D017646:Organosilicon Compounds; D004986:Ether; C116609:3-hydroxybutanal