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Catalytic Carbonyl-Olefin Metathesis of Aliphatic Ketones: Iron(III) Homo-Dimers as Lewis Acidic Superelectrophiles

Author:
Albright, Haley, Riehl, Paul S., McAtee, Christopher C., Reid, Jolene P., Ludwig, Jacob R., Karp, Lindsey A., Zimmerman, Paul M., Sigman, Matthew S., Schindler, Corinna S.
Source:
Journal of the American Chemical Society 2018 v.141 no.4 pp. 1690-1700
ISSN:
1520-5126
Subject:
Lewis acids, catalysts, catalytic activity, chemical bonding, iron, ketones
Abstract:
Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon–carbon bond formation. However, currently available synthetic protocols rely exclusively on aryl ketone substrates while the corresponding aliphatic analogs remain elusive. We herein report the development of Lewis acid-catalyzed carbonyl-olefin ring-closing metathesis reactions for aliphatic ketones. Mechanistic investigations are consistent with a distinct mode of activation relying on the in situ formation of a homobimetallic singly bridged iron(III)-dimer as the postulated active catalytic species. These “superelectrophiles” function as more powerful Lewis acid catalysts that form upon association of individual iron(III)-monomers. While this mode of Lewis acid activation has previously been postulated to exist, it has not yet been applied in a catalytic setting. The insights presented are expected to enable further advancement in Lewis acid catalysis by building upon the activation principle of “superelectrophiles” and to broaden the current scope of catalytic carbonyl-olefin metathesis reactions.
Agid:
6288089