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.