Lewis Acid Activation of the Ferrous Heme–NO Fragment toward the N–N Coupling Reaction with NO To Generate N2O

<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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Convergent Synthesis of Immune Inhibitor IMMH002

Synthesis ◽

10.1055/s-0040-1706299 ◽

2020 ◽

Author(s):

Qiong Xiao ◽

Si Chen ◽

Zeyu Shi ◽

Dali Yin

Keyword(s):

Environmental Impact ◽

Lewis Acid ◽

Column Chromatography ◽

Coupling Reaction ◽

Cross Coupling ◽

Convergent Synthesis ◽

Quality Problem ◽

Cross Coupling Reaction

AbstractA convergent synthesis of IMMH002 in 36% overall yield starting from bromobenzene is described with a key Suzuki–Miyaura cross-coupling reaction used to provide a crucial intermediate. The route does not require column chromatography and solves the most intractable quality problem caused by a homologue by-product in the original linear synthesis. Furthermore, reducing the use of Lewis acid mediated reactions improves the environmental impact of the synthesis and reduces overall waste. The new route described herein is more efficient, convenient, reliable, and economically more viable when compared to the previously reported linear route.

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Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

Chemistry - A European Journal ◽

10.1002/chem.201901163 ◽

2019 ◽

Vol 25 (35) ◽

pp. 8371-8386 ◽

Cited By ~ 1

Author(s):

Irene Erdelmeier ◽

Gerd Bülow ◽

Chang‐Wan Woo ◽

Jürgen Decker ◽

Gerhard Raabe ◽

...

Keyword(s):

Lewis Acid ◽

Coupling Reaction ◽

Cross Coupling ◽

Nickel Catalysis ◽

Cross Coupling Reaction

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Efficient Phosphodiester Binding and Cleavage by a ZnII Complex Combining Hydrogen-Bonding Interactions and Double Lewis Acid Activation

Angewandte Chemie International Edition ◽

10.1002/anie.200602532 ◽

2006 ◽

Vol 45 (42) ◽

pp. 7056-7059 ◽

Cited By ~ 97

Author(s):

Guoqiang Feng ◽

Daniela Natale ◽

Ravi Prabaharan ◽

Juan C. Mareque-Rivas ◽

Nicholas H. Williams

Keyword(s):

Hydrogen Bonding ◽

Lewis Acid ◽

Acid Activation ◽

Hydrogen Bonding Interactions

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Hydrosilylation of Carbonyls Catalyzed by Hydridoborenium Borate Salts: Lewis Acid Activation and Anion Mediated Pathways

Inorganic Chemistry ◽

10.1021/acs.inorgchem.0c00646 ◽

2020 ◽

Vol 59 (10) ◽

pp. 7195-7203 ◽

Cited By ~ 2

Author(s):

Sandeep Rawat ◽

Mamta Bhandari ◽

Vishal Kumar Porwal ◽

Sanjay Singh

Keyword(s):

Lewis Acid ◽

Acid Activation ◽

Borate Salts

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A coupling reaction between tetrahydrofuran and olefins by Rh-catalyzed/Lewis acid-promoted C–H activation

Tetrahedron Letters ◽

10.1016/j.tetlet.2008.05.057 ◽

2008 ◽

Vol 49 (31) ◽

pp. 4652-4654 ◽

Cited By ~ 14

Author(s):

Ke Cao ◽

Yi-Jun Jiang ◽

Shu-Yu Zhang ◽

Chun-An Fan ◽

Yong-Qiang Tu ◽

...

Keyword(s):

Lewis Acid ◽

Coupling Reaction

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Ru alkylidene compounds bearing tridentate, dianionic ligands: Lewis acid activation and olefin metathesis

Dalton Transactions ◽

10.1039/c5dt04481b ◽

2016 ◽

Vol 45 (9) ◽

pp. 3844-3852 ◽

Cited By ~ 4

Author(s):

Adam M. McKinty ◽

Douglas W. Stephan

Keyword(s):

Lewis Acid ◽

Olefin Metathesis ◽

Acid Activation ◽

Dianionic Ligands

The series of tridentate complexes were prepared and shown to react with BCl3 to give the complexes affording neutral and cationic complexes sequentially. The generated five coordinate cations were evaluated in standard preliminary tests for olefin metathesis catalysis.

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