Synthesis and C-alkylation of hindered aldehyde enamines.
A new reactivity mode of hindered lithium amides with terminal epoxides is described whereby aldehyde enamines are produced via a previously unrecognized reaction pathway. Some of these aldehyde enamines display unprecedented C-alkylation reactivity toward unactivated primary and secondary alkyl halides. For comparison, the reactivity of aldehyde enamines synthesized via a traditional condensation method was examined. C- rather than N-alkylation was the dominant reaction pathway found with a range of electrophiles, making this route to alpha-alkylated aldehydes more synthetically useful than previously reported.
Hodgson
David M
DM
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK. david.hodgson@chem.ox.ac.uk
Bray
Christopher D
CD
Kindon
Nicholas D
ND
Reynolds
Nigel J
NJ
Coote
Steven J
SJ
Um
Joann M
JM
Houk
K N
KN
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000478:Alkylation; D000577:Amides / Q000737:chemistry; D004852:Epoxy Compounds / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry
D000447:Aldehydes; D000577:Amides; D004852:Epoxy Compounds; D009942:Organometallic Compounds; D008094:Lithium