4.8 Article

Dinuclear Cobalt Complex-Catalyzed Stereodivergent Semireduction of Alkynes: Switchable Selectivities Controlled by H2O

Journal

ACS CATALYSIS
Volume 11, Issue 21, Pages 13696-13705

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c04141

Keywords

dinuclear cobalt; stereodivergent semihydrogenation; switchable selectivities; alkynes; H2O

Funding

  1. National Natural Science Foundation of China [21821002, 21890722, 21950410519, 21702109]
  2. Shanghai Pujiang Program [19PJ1411500]
  3. Natural Science Foundation of Tianjin Municipality [19JCJQJC62300, 18JCYBJC21400]
  4. Tianjin Research Innovation Project for Postgraduate Students [2019YJSB081]
  5. Frontiers Science Center for New Organic Matter [Nankai University] [63181206]
  6. Fundamental Research Funds for Central Universities (Nankai University)

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The switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand allows control of the stereoisomerization process by adjusting the amount of water, providing a convenient method for obtaining either (Z)- or (E)-olefin isomer in a single transformation.
Catalytic semireduction of internal alkynes to alkenes is very important for organic synthesis. Although great success has been achieved in this area, switchable Z/E stereoselectivity based on a single catalyst for the semireduction of internal alkynes is a longstanding challenge due to the multichemo- and stereoselectivity, especially based on less-expensive earth-abundant metals. Herein, we describe a switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand. It was found that cis-reduction of the alkyne occurs first and the Z-E alkene stereoisomerization process is formally controlled by the amount of H2O, since the concentration of H2O may influence the catalytic activity of the catalyst for isomerization. Therefore, this protocol provides a the (Z)- or (E)-olefin isomer in a single transformation by adjusting the amount of water.

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