Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States.
J Am Chem Soc. 2021 Aug 25;143(33):13370-13381. doi: 10.1021/jacs.1c06528. Epub 2021 Aug 10.
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.
二异丙基胺钠（NaDA）在二甲基乙胺（DMEA）和 DMEA-碳氢化合物混合物中与添加的 ，，′′，′′-五甲基二亚乙基三胺（PMDTA）反应，可与烷基卤化物、环氧化物、腙、芳烃、烯烃和烯丙基醚反应。PMDTA 与 ，，，′′-四甲基乙二胺（TMEDA）的比较，同时进行详细的速率和计算研究，揭示了三官能性和 κ-κ 半配位的重要性。速率研究表明，2-溴辛烷、环辛烯氧化物和二甲间苯二酚的反应均仅基于单体。用 10 mol% PMDTA 催化，在 10 次转化中没有抑制作用的情况下，反应速度最高可加速 >30 倍（>300）。固-液相转移催化（SLPTC）被探索作为优化催化以及探索非均相反应条件的优点的一种手段。
