Work

Non-Innocent Role of Sacrificial Anodes in Electrochemical Nickel-Catalyzed C(sp 2 )–C(sp 3 ) Cross-Electrophile Coupling

Year: 2024

Type: article

Abstract: Sacrificial anodes composed of inexpensive metals such as Zn, Fe, and Mg are widely used to support electrochemical nickel-catalyzed cross-electrophile coupling (XEC) reactions, in addition to other reductive electrochemical transformations. Such anodes are appealing because they provide a stable counter-electrode potential and typically avoid interference with the reductive chemistry. The present study outlines the development of an electrochemical Ni-catalyzed XEC reaction that streamlines access to a key pharmaceutical intermediate. Metal ions derived from sacrificial anode oxidation, however, directly contribute to homocoupling and proto-dehalogenation side products that are commonly formed in chemical and electrochemical Ni-catalyzed XEC reactions. Use of a divided cell limits interference by the anode-derived metal ions and supports a high product yield with negligible side product formation, introducing a strategy to overcome one of the main limitations of Ni-catalyzed XEC.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c10979

Authors: Luana Cardinale, Gregory L. Beutner, Christopher Y. Bemis, Daniel J. Weix, Shannon S. Stahl

Institutions: University of Wisconsin–Madison, Bristol-Myers Squibb (United States)

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, Bristol-Myers Squibb, National Institutes of Health, National Institute of General Medical Sciences

Awards: Collaborative Research: Electrochemical Ni-Catalyzed Reductive Biaryl Coupling: Mechanistic Studies to Enable Chemical Synthesis, Acquisition of a 400 MHz NMR Spectrometer for Chemical Research and Learning, Laser-Enhanced NMR Instrumentation for Chemical and Biochemical Research, G7119203849