10.1021/jacs.7b08734.s001
Russell
F. Algera
Russell
F.
Algera
Yun Ma
Yun
Ma
David B. Collum
David B.
Collum
Sodium
Diisopropylamide in Tetrahydrofuran: Selectivities,
Rates, and Mechanisms of Arene Metalations
American Chemical Society
2017
trisolvated monomer-based metalations
rate studies
Arene Metalations Sodium diisopropylamide
THF
monosubstituted arenes
methoxylated arenes show
2017-09-26 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Sodium_Diisopropylamide_in_Tetrahydrofuran_Selectivities_Rates_and_Mechanisms_of_Arene_Metalations/5501764
Sodium
diisopropylamide (NaDA)-mediated metalations of arenes in
tetrahydrofuran (THF)/hexane or THF/Me<sub>2</sub>NEt solutions are
described. A survey of >40 benzenoid- and pyridine-based arenes
with
a range of substituents demonstrates the efficacy and regioselectivity
of metalation. Metalations of activated disubstituted arenes and selected
monosubstituted arenes are rapid at −78 °C. Rate studies
of 1,3-dimethoxybenzene and related methoxylated arenes show exclusively
monomer-based orthometalations with two or three coordinated THF ligands.
Rate studies of the isotopic exchange of benzene and monosubstituted
arenes with weakly activating groups reveal analogous di- and trisolvated
monomer-based metalations. Cooperative inductive, mesomeric, steric,
and chelate effects are discussed.