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Aliphatic Carbonyl-Olefin Metathesis.pdf (2.14 MB)

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

preprint
submitted on 25.09.2018, 21:51 and posted on 26.09.2018, 14:06 by Haley Albright, Paul S. Riehl, Christopher C. McAtee, Jolene P. Reid, Jacob R. Ludwig, Lindsey A. Karp, Paul M. Zimmerman, Matthew S. Sigman, Corinna S. Schindler
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 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 broaden the current scope of catalytic carbonyl-olefin metathesis reactions.

Funding

R01-GM118644, CHE-1551994, DGE 1256260, CHE-1763436, ACI-1548562

History

Email Address of Submitting Author

haalbri@umich.edu

Institution

University of Michigan

Country

United States

ORCID For Submitting Author

0000-0003-2496-5360

Declaration of Conflict of Interest

No conflict of interest.

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