4.7 Article

CV-driven Optimization: Cobalt-Catalyzed Electrochemical Expedient Oxychlorination of Alkenes via ORR

Journal

ADVANCED SYNTHESIS & CATALYSIS
Volume 361, Issue 24, Pages 5626-5633

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.201901260

Keywords

cyclic voltammetry; chemical trial-and-error; electrochemistry; oxygen reduction reaction; persistent radical effect; screening method

Funding

  1. Foundation of State Key Laboratory of Biobased Material and Green Papermaking [ZZ20190312]
  2. Qilu University of Technology (Shandong Academy of Sciences) [0412048811, 81110326]
  3. Shandong Provincial Natural Science Foundation [ZR2018BB017]
  4. National Natural Science Foundation of China [21801144, 81872744, 51602164]
  5. Youth Innovative Talents Recruitment and Cultivation Program of Shandong Higher Education
  6. Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Province

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Instead of screening reaction conditions by yield-based chemical trial-and-error, potential-based cyclic voltammetry was alternatively employed for optimization of electrochemical oxychlorination of alkenes. With this unconventional screening method, the catalyst system including catalysts, molar ratio of chloride sources and solvents were identified in a rational, time- and energy-efficient manner. The optimal catalytic system in combination with oxygen reduction reaction enabled broad substrate scopes for the desired transformation by taking advantages of persistent radical effect. UV-vis and CV titration experiments confirmed the in-situ formed catalytic species [CoCl5]. Moreover, cyclic voltammetry was applied to obtain mechanistic insights in our reaction system.

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