Lewis Acid Catalyzed Carbonyl–Olefin Metathesis

<div>Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon-carbon bond</div><div>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.</div>

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ChemInform Abstract: A NOVEL CARBON-CARBON BOND FORMATION BY THE LEWIS ACID CATALYZED REACTION OF β-STYRYLSILANE WITH ACETAL

Chemischer Informationsdienst ◽

10.1002/chin.198204155 ◽

1982 ◽

Vol 13 (4) ◽

Author(s):

T. HIRAO ◽

S. KOHNO ◽

J. ENDA ◽

Y. OHSHIRO ◽

T. AGAWA

Keyword(s):

Lewis Acid ◽

Bond Formation ◽

Carbon Bond ◽

Carbon Carbon Bond ◽

Acid Catalyzed

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

10.26434/chemrxiv.7130801 ◽

2018 ◽

Cited By ~ 1

Author(s):

Haley Albright ◽

Paul S. Riehl ◽

Christopher C. McAtee ◽

Jolene P. Reid ◽

Jacob R. Ludwig ◽

...

Keyword(s):

Lewis Acid ◽

Olefin Metathesis ◽

Acid Activation ◽

Lewis Acid Catalysts ◽

Distinct Mode ◽

Aliphatic Ketones ◽

Carbon Carbon Bond ◽

Metathesis Reactions ◽

Acid Catalyzed

<div>Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon-carbon bond</div><div>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.</div>

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