Catalytic metal-free intramolecular hydroaminations of non-activated aminoalkenes: a computational exploration

Dalton Transactions : an International Journal of Inorganic Chemistry
Haixia LiZhi-Xiang Wang

Abstract

Frustrated Lewis pairs (FLPs) has been applied to catalytic metal-free hydrogenation. Can the FLP reactivity be used for catalytic hydroamination? Using density functional theory (DFT) calculations, we have explored whether the molecules cat1-cat3, which were previously designed by integrating the dearomatization-aromatization effect and the FLP reactivity, can catalyze the intramolecular hydroaminations of non-activated aminoalkenes to afford nitrogen heterocycles. The study shows that the γ-aminoalkene (am1) hydroamination catalyzed by cat1 proceeds via two steps (aminoalkene N-H bond activation and C-N bond formation) with experimentally accessible energetics, giving the five-membered nitrogen heterocycle product 1,1-dimethylpyrrolidine. The N-H bond activation is reversible. The C-N bond formation step undergoes a concerted mechanism and complies with the Markovnikov addition rule. Possible side reactions which may cause catalyst deactivation were confirmed to be energetically unfavorable. The molecules cat2 and cat3 are less effective than cat1 in catalyzing the am1 hydroamination, but the barriers are not too high. By following the most favorable pathway of the cat1-mediated am1 hydroamination, we further extended the sub...Continue Reading

References

Feb 14, 2002·Journal of the American Chemical Society·Ulrike Nettekoven, John F Hartwig
Feb 19, 2002·Chemical Reviews·Thomas E. Müller, Matthias Beller
Jun 13, 2002·Chemical Reviews·Gary A Molander, Jan Antoinette C Romero
Apr 10, 2003·Chemical Society Reviews·Frauke Pohlki, Sven Doye
Jul 17, 2004·Organic Letters·Lutz AckermannChristian J Gschrei
Sep 24, 2004·Accounts of Chemical Research·Sukwon Hong, Tobin J Marks
Jan 27, 2005·Journal of the American Chemical Society·Christopher F Bender, Ross A Widenhoefer
Mar 1, 2006·Chemical Society Reviews·Joseph S M SamecPeter Brandt
Nov 18, 2006·Science·Gregory C WelchDouglas W Stephan
Jan 31, 2007·Journal of the American Chemical Society·Gregory C Welch, Douglas W Stephan
Oct 27, 2007·Accounts of Chemical Research·Takao Ikariya, A John Blacker
Nov 7, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Isabelle AillaudEmmanuelle Schulz
Jan 12, 2008·Accounts of Chemical Research·Yan Zhao, Donald G Truhlar
Mar 28, 2008·Chemical Communications : Chem Comm·Preston A ChaseDouglas W Stephan
Apr 19, 2008·Organic & Biomolecular Chemistry·Douglas W Stephan
Aug 30, 2008·Chemical Reviews·Thomas E MüllerMizuki Tada
Oct 2, 2008·Journal of the American Chemical Society·Victor SumerinBernhard Rieger
Jan 23, 2009·Journal of the American Chemical Society·Tibor András RokobImre Pápai
Feb 20, 2009·Journal of the American Chemical Society·Kirill V AxenovGerhard Erker
May 8, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Douglas W Stephan
May 26, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Timofei Privalov
Jun 26, 2009·Journal of the American Chemical Society·Mark R CrimminPanayiotis A Procopiou
Sep 16, 2009·Chemical Communications : Chem Comm·Chunfang JiangHeinz Berke
Sep 25, 2009·Journal of the American Chemical Society·Erin MorganLaura Turculet
Oct 28, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Mark A IronDavid Milstein
Dec 5, 2009·Journal of the American Chemical Society·Xinzheng Yang, Michael B Hall
Dec 22, 2009·Angewandte Chemie·Douglas W Stephan, Gerhard Erker

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Citations

Nov 13, 2013·The Journal of Organic Chemistry·Akhilesh K VermaKeykavous Parang
Sep 16, 2016·Journal of the American Chemical Society·Urs GellrichDavid Milstein
Feb 22, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Xing-Yu SunXiao-Bing Lu
May 26, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Zheyuan LiuZhi-Xiang Wang
Apr 25, 2019·Inorganic Chemistry·Hugh B HamiltonDuncan F Wass

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