Reactions\nof Sodium Diisopropylamide: Liquid-Phase\nand Solid–Liquid Phase-Transfer Catalysis by <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>″,<i>N</i>″‑Pentamethyldiethylenetriamine

Abstract

Sodium\ndiisopropylamide (NaDA) in dimethylethylamine (DMEA) and\nDMEA–hydrocarbon mixtures with added <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>″,<i>N</i>″-pentamethyldiethylene triamine (PMDTA) reacts\nwith alkyl halides, epoxides, hydrazones, arenes, alkenes, and allyl\nethers. Comparisons of PMDTA with <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetramethylethylenediamine\n(TMEDA) accompanied by detailed rate and computational studies reveal\nthe importance of the trifunctionality and κ²–κ³ hemilability. Rate studies show exclusively monomer-based\nreactions of 2-bromooctane, cyclooctene oxide, and dimethylresorcinol.\nCatalysis with 10 mol % PMDTA shows up to >30-fold accelerations\n(<i>k</i>_cat > 300) with no evidence of inhibition\nover\n10 turnovers. Solid–liquid phase-transfer catalysis (SLPTC)\nis explored as a means to optimize the catalysis as well as explore\nthe merits of heterogeneous reaction conditions.