The Origin of Anti-Markovnikov Regioselectivity in Alkene Hydroamination Reactions Catalyzed by [Rh(DPEphos)]+

Almudena Couce-Rios, Agustí Lledós, Gregori Ujaque

Research output: Contribution to journalArticleResearchpeer-review

21 Citations (Scopus)

Abstract

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim The development of regioselective anti-Markovnikov alkene's hydroamination is a long-standing goal in catalysis. The [Rh(COD)(DPEphos)]+complex is the most general and regioselective group 9 catalyst for such a process. The reaction mechanism for intermolecular hydroamination of alkenes catalyzed by [Rh(DPEphos)]+complex is analyzed by means of DFT calculations. Hydroamination (alkene vs. amine activation routes) as well as oxidative amination pathways are analyzed. According to the computational results the operating mechanism can be generally described by alkene coordination, amine nucleophilic addition, proton transfer through the metal center and reductive elimination steps. The mechanism for the formation of the oxidative amination side product goes via a β-elimination after the nucleophilic addition and metal center protonation steps. The origin of the regioselectivity for the addition process (Markovnikov vs. anti-Markovnikov additions) is shown to be not charge but orbitally driven. Remarkably, η2to η1slippage degree on the alkene coordination mode is directly related to the regioselective outcome.
Original languageEnglish
Pages (from-to)9311-9320
JournalChemistry - A European Journal
Volume22
Issue number27
DOIs
Publication statusPublished - 1 Jan 2016

Keywords

  • hydroamination
  • nucleophilic attack
  • oxidative amination
  • rhodium
  • styrene

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