n-Butyllithium/N,N,N',N'-tetramethylethylenediamine-mediated ortholithiations of aryl oxazolines: substrate-dependent mechanisms.
n-Butyllithium/N,N,N',N'-tetramethylethylenediamine-mediated ortholithiations of aryloxazolines are described. Methyl substituents on the aryloxazoline and substituents at the meta position of the arenes (methoxy, oxazolinyl, and fluoro) influence the rates and the mechanisms. Monomer- and dimer-based reactions are implicated. Density functional calculations probe details of the mechanism and suggest the origins of cooperative effects in meta-substituted aryl oxazolines.
Chadwick
Scott T
ST
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.
Ramirez
Antonio
A
Gupta
Lekha
L
Collum
David B
DB
D005029:Ethylenediamines / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010080:Oxazoles / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
D005029:Ethylenediamines; D009942:Organometallic Compounds; D010080:Oxazoles; C005798:N,N,N',N'-tetramethylethylenediamine; D008094:Lithium