TY - JOUR
T1 - Plasma Electrochemistry for Carbon-Carbon Bond Formation via Pinacol Coupling
AU - Wang, Jian
AU - Üner, Necip B.
AU - Dubowsky, Scott Edwin
AU - Confer, Matthew P.
AU - Bhargava, Rohit
AU - Sun, Yunyan
AU - Zhou, Yuting
AU - Sankaran, R. Mohan
AU - Moore, Jeffrey S.
N1 - Funding Information:
This work was financially supported by the Swiss National Science Foundation (SNSF) P2ELP2_195130 and P500PN_210792, and the Air Force Office of Scientific Research under Grant No. FA9550-19-1-0088. M.P.C. acknowledges a U.S. National Science Foundation (NSF) Division of Ocean Sciences Postdoctoral Fellowship (Award Number 2205819).
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/5/17
Y1 - 2023/5/17
N2 - The formation of carbon-carbon bonds by pinacol coupling of aldehydes and ketones requires a large negative reduction potential, often realized with a stoichiometric reducing reagent. Here, we use solvated electrons generated via a plasma-liquid process. Parametric studies with methyl-4-formylbenzoate reveal that selectivity over the competing reduction to the alcohol requires careful control over mass transport. The generality is demonstrated with benzaldehydes, benzyl ketones, and furfural. A reaction-diffusion model explains the observed kinetics, and ab initio calculations provide insight into the mechanism. This study opens the possibility of a metal-free, electrically-powered, sustainable method for reductive organic reactions.
AB - The formation of carbon-carbon bonds by pinacol coupling of aldehydes and ketones requires a large negative reduction potential, often realized with a stoichiometric reducing reagent. Here, we use solvated electrons generated via a plasma-liquid process. Parametric studies with methyl-4-formylbenzoate reveal that selectivity over the competing reduction to the alcohol requires careful control over mass transport. The generality is demonstrated with benzaldehydes, benzyl ketones, and furfural. A reaction-diffusion model explains the observed kinetics, and ab initio calculations provide insight into the mechanism. This study opens the possibility of a metal-free, electrically-powered, sustainable method for reductive organic reactions.
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U2 - 10.1021/jacs.3c01779
DO - 10.1021/jacs.3c01779
M3 - Article
C2 - 37146270
AN - SCOPUS:85159604108
SN - 0002-7863
VL - 145
SP - 10470
EP - 10474
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 19
ER -