69621-97-2Relevant academic research and scientific papers
Ortho Metalation Directed by α-Amino Alkoxides
Comins, Daniel L.,Brown, Jack D.
, p. 1078 - 1083 (1984)
The addition of aromatic aldehydes to certain lithium dialkylamides in benzene or tetrahydrofuran gave α-amino alkoxides which were ortho lithiated with excess n-butyllithium.Subsequent alkylation and hydrolysis provided ortho-substituted aromatic aldehydes via a one-pot reaction.The ortho metalation of α-amino alkoxides derived from 1- and 2-naphthaldehyde and various substituted benzaldehydes was examined.When N,N,N'-trimethylethylenediamine was used as the amine component of the α-amino alkoxide, metalation could be carried out at lower temperatures.This rate increase is due to an intramolecular TMEDA-like assisted metalation.The synthetic utility of this ortho metalation, including how varying the amine component of the α-amino alkoxide affects the regiochemistry and metalation rate, is discussed.
