Reactions of Sodium Diisopropylamide: Liquid-Phase and Solid-Liquid Phase-Transfer Catalysis by ,,',″,″-Pentamethyldiethylenetriamine

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Aug 10

PMID 34375095

Citations 4

Authors

Yun Ma

Ryan A Woltornist

Russell F Algera

David B Collum

Affiliations

Soon will be listed here.

Abstract

Sodium diisopropylamide (NaDA) in ,-dimethylethylamine (DMEA) and DMEA-hydrocarbon mixtures with added ,,',″,″-pentamethyldiethylenetriamine (PMDTA) reacts with alkyl halides, epoxides, hydrazones, arenes, alkenes, and allyl ethers. Comparisons of PMDTA with ,,','-tetramethylethylenediamine (TMEDA) accompanied by detailed rate and computational studies reveal the importance of the trifunctionality and κ-κ hemilability. Rate studies show exclusively monomer-based reactions of 2-bromooctane, cyclooctene oxide, and dimethylresorcinol. Catalysis with 10 mol % PMDTA shows up to >30-fold accelerations ( > 300) with no evidence of inhibition over 10 turnovers. Solid-liquid phase-transfer catalysis (SLPTC) is explored as a means to optimize the catalysis as well as explore the merits of heterogeneous reaction conditions.

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