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Title: Reductive samarium (electro)catalysis enabled by Sm III -alkoxide protonolysis
Samarium diiodide (SmI2) is a privileged, single-electron reductant deployed in diverse synthetic settings. However, generalizable methods for catalytic turnover remain elusive because of the well-known challenge associated with cleaving strong SmIII–O bonds. Prior efforts have focused on the use of highly reactive oxophiles to enable catalyst turnover. However, such approaches give rise to complex catalyst speciation and intrinsically limit the synthetic scope. Herein, we leveraged a mild and selective protonolysis strategy to achieve samarium-catalyzed, intermolecular reductive cross-coupling of ketones and acrylates with broad scope. The modularity of our approach allows rational control of selectivity based on solvent, pKa(whereKais the acid dissociation constant), and the samarium coordination sphere and provides a basis for future developments in catalytic and electrocatalytic lanthanide chemistry.  more » « less
Award ID(s):
2002158
PAR ID:
10535434
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
American Association for the Advancement of Science
Date Published:
Journal Name:
Science
Volume:
385
Issue:
6711
ISSN:
0036-8075
Page Range / eLocation ID:
847 to 853
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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