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<p>One of the most direct methods for synthesizing internal alkenes is the isomerization of terminal alkenes. Currently, noble metal catalysts are the most commonly used for alkene isomerization. However, the high cost and limited availability of late transition metals have prompted growing interest in replacing these precious metals with more readily available, earth-abundant alternatives. Herein, we report an iron-catalyzed alkene isomerization conducted in absence of solvent. A well-defined mononuclear Fe(II) complex, [HFe(CO)<sub>4</sub>SiPh<sub>3</sub>] ([<b>Fe-1</b>]), efficiently catalyzes the isomerization of terminal alkenes to internal alkenes under mild conditions. To demonstrate the synthetic utility of this transformation, gram-scale isomerization reactions were successfully performed. Kinetic investigations reveal that the reaction follows approximately first-order kinetics with respect to the iron catalyst, with an initial reaction rate of 7.08 × 10<sup>-3</sup> Mmin<sup>-1</sup>. Furthermore, the tandem functionalization of terminal alkenes to aldehyde products was achieved via sequential isomerizing-ozonolysis and isomerizing-hydroformylation reactions. The complementarity of the two catalysts (Fe and Rh) was conclusively demonstrated through mechanistic investigations and control experiments.</p><p></p>

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Iron-catalyzed alkene isomerization and tandem functionalization

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年4月24日

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  • Rohit Kumar,
  • Anirban Sen,
  • Tanuja Tewari,
  • Suhas T. Parit,
  • Kishor V. Khopade,
  • Samir H. Chikkali

摘要

One of the most direct methods for synthesizing internal alkenes is the isomerization of terminal alkenes. Currently, noble metal catalysts are the most commonly used for alkene isomerization. However, the high cost and limited availability of late transition metals have prompted growing interest in replacing these precious metals with more readily available, earth-abundant alternatives. Herein, we report an iron-catalyzed alkene isomerization conducted in absence of solvent. A well-defined mononuclear Fe(II) complex, [HFe(CO)4SiPh3] ([Fe-1]), efficiently catalyzes the isomerization of terminal alkenes to internal alkenes under mild conditions. To demonstrate the synthetic utility of this transformation, gram-scale isomerization reactions were successfully performed. Kinetic investigations reveal that the reaction follows approximately first-order kinetics with respect to the iron catalyst, with an initial reaction rate of 7.08 × 10-3 Mmin-1. Furthermore, the tandem functionalization of terminal alkenes to aldehyde products was achieved via sequential isomerizing-ozonolysis and isomerizing-hydroformylation reactions. The complementarity of the two catalysts (Fe and Rh) was conclusively demonstrated through mechanistic investigations and control experiments.