General C(sp2)-C(sp3) Cross-Electrophile Coupling Reactions Enabled by Overcharge Protection of Homogeneous Electrocatalysts

Article abstract of DOI:10.1021/jacs.0c01475

Cross-electrophile coupling (XEC) of alkyl and aryl halides promoted by electrochemistry represents an attractive alternative to conventional methods that require stoichiometric quantities of high-energy reductants. Most importantly, electroreduction can readily exceed the reducing potentials of chemical reductants to activate catalysts with improved reactivities and selectivities over conventional systems. This work details the mechanistically-driven development of an electrochemical methodology for XEC that utilizes redox-active shuttles developed by the energy-storage community to protect reactive coupling catalysts from overreduction. The resulting electrocatalytic system is practical, scalable, and broadly applicable to the reductive coupling of a wide range of aryl, heteroaryl, or vinyl bromides with primary or secondary alkyl bromides. The impact of overcharge protection as a strategy for electrosynthetic methodologies is underscored by the dramatic differences in yields from coupling reactions with added redox shuttles (generally >80%) and those without (generally <20%). In addition to excellent yields for a wide range of substrates, reactions protected from overreduction can be performed at high currents and on multigram scales.

Full text of DOI:10.1021/jacs.0c01475

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Article
General C(sp2)-C(sp3) Cross-Electrophile Coupling Reactions
Enabled by Overcharge Protection of Homogeneous Electrocatalysts
Blaise L. Truesdell, Taylor B. Hamby, and Christo S. Sevov
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c01475 • Publication Date (Web): 29 Feb 2020
Downloaded from pubs.acs.org on February 29, 2020
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Journal of the American Chemical Society
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ACS Paragon Plus Environment

Page 7 of 13
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 8 of 13
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ACS Paragon Plus Environment

Page 9 of 13
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 10 of 13
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ACS Paragon Plus Environment

Page 11 of 13
Journal of the American Chemical Society
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ACS Paragon Plus Environment

Journal of the American Chemical Society
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Journal of the American Chemical Society
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