4.8 Article

Mn-Catalyzed Electrooxidative Undirected C-H/P-H Cross-Coupling between Aromatics and Diphenyl Phosphine Oxides

Journal

ACS CATALYSIS
Volume 11, Issue 7, Pages 4295-4300

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c00549

Keywords

transition-metal catalysis; C-P bond formation; electrochemistry; phosphorylation; hydrogen evolution

Funding

  1. National Natural Science Foundation of China [21520102003, 21701127, 21702150]
  2. Hubei Province Natural Science Foundation of China [2017CFA010]
  3. Program of Introducing Talents of Discipline to Universities of China (111 Program)

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A manganese-catalyzed electrochemical intermolecular dehydrogenative cross-coupling reaction between aryl C-H and diphenyl phosphine oxides was reported in this study. By adjusting the proportion of substrates, a series of phosphorylation or diphosphorylation products could be obtained separately, without the need for external chemical oxidants. The research also indicated that C-H activation was not the rate-determining step.
C-P bonds are widely found in a great many bioactive compounds and functional molecules. Transition-metal-catalyzed dehydrogenative C-H/P-H cross-coupling plays a crucial part in C-P bond formation since it requires no pretreatment of substrates. Herein, we reported a Mncatalyzed electrochemical intermolecular dehydrogenative cross-coupling between aryl C-H and diphenyl phosphine oxides. In undivided cells, a series of phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion of substrates. A catalytic amount of inexpensive Mn(II) salt was used, and no external chemical oxidants were needed in this process. A kinetic isotope effect experiment suggested that the C-H activation was not the rate-determining step.

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