Synlett 2019; 30(10): 1187-1193
DOI: 10.1055/s-0037-1611792
cluster
© Georg Thieme Verlag Stuttgart · New York

Phthalocyanines as a π–π Adsorption Strategy to Immobilize Catalyst on Carbon for Electrochemical Synthesis

Kevin J. Klunder
a   Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA   Email: minteer@chem.utah.edu
b   Center for Synthetic Organic Electrochemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA
,
Ashley C. Cass
a   Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA   Email: minteer@chem.utah.edu
b   Center for Synthetic Organic Electrochemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA
,
Scott L. Anderson
a   Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA   Email: minteer@chem.utah.edu
b   Center for Synthetic Organic Electrochemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA
,
a   Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA   Email: minteer@chem.utah.edu
b   Center for Synthetic Organic Electrochemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA
› Author Affiliations
The authors would like to thank the Division of Chemistry (1740656) and the National Science Foundation Center for Synthetic Organic Electrochemistry for funding (CHE-1740656).
Further Information

Publication History

Received: 04 February 2019

Accepted after revision: 24 March 2019

Publication Date:
18 April 2019 (online)


Published as part of the Cluster Electrochemical Synthesis and Catalysis

Abstract

In most electrochemical syntheses, reactions are happening at or near the electrode surface. For catalyzed reactions, ideally, the electrode surface would solely contain the catalyst, which then simplifies purification and lowers the amount of catalyst needed. Here, a new strategy involving phthalocyanines (Pc) to immobilize catalysts onto carbon electrode surfaces is presented. The large π structure of the Pc enables adsorption to the sp2-structure of graphitic carbon. TEMPO-modified Pc were chosen as a proof of concept to test the new immobilization strategy. It was found that the TEMPO-Pc derivatives functioned similarly or better than the widely used pyrene adsorption method. Interestingly, the new TEMPO-Pc catalyst appears to facilitate a cascade reaction involving both the anode and the cathode. The first step is the generation of an aryl aldehyde (anode) followed by the reduction of the aryl aldehyde in a pinacol-type coupling reaction at the cathode. The last step is the oxidation of a hydrobenzoin to create benzil. This work demonstrates the unique ability of electrochemistry and bifunctional catalysts to enable multistep chemical transformations, performing both reductive and oxidative transformations in one pot.

Supporting Information

 
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