Iron-Catalyzed Dehydrogenative sp<sup>3</sup>–sp<sup>2</sup> Coupling via Direct Oxidative C–H Activation of Acetonitrile

Su, Huimin; Wang, Luyao; Rao, Honghua; Xu, Hao

doi:10.1021/acs.orglett.7b00678

Cited by 92 publications

(31 citation statements)

References 74 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…They reported a direct synthesis of α‐cyanomethyl‐β‐dicarbonyl compounds 41 by oxidative coupling of acetonitrile and 1,3‐dicarbonyl compounds 40 (Scheme , second from top). A related iron‐catalyzed dehydrogenative coupling of CH 3 CN and 2‐arylimidazo[1,2‐ a ]pyridine was investigated by Rao and Xu; the coupling products could be further elaborated to the pharmaceutical zolpidem . An iron catalyzed aerobic oxidative C–CN bond cleavage reaction leading to various esters has also recently been reported …”

Section: Cross Dehydrogenative Coupling Reactionsmentioning

confidence: 99%

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Bauer

2017

Israel Journal of Chemistry

View full text Add to dashboard Cite

Iron-catalyzed oxidation reactions have been increasingly investigated in the past two decades and have seen a major increase in research activity. This review article demonstrates the vigorous research activities in the field based on examples from the most recent literature. Catalyst systems are discussed that are active in the oxygenation of alkanes and alkenes to obtain alcohols, ketones or epoxides. Iron-catalyzed oxidation of alcohols to the corresponding carbonyl units are also included. Enantioselective and heterogeneous catalyst systems are presented as well, and a brief overview of mechanistic pictures is given. B. Bauer was born in Nuremberg, Germany. He received PhD degree in 2003 from the University of Erlangen-Nuremberg; under the supervision of Prof. John A. Gladysz, he performed ring closing metathesis reactions in the coordination sphere of transition metals to obtain macrocyclic metal complexes. He performed postdoctoral research at the University of California, Riverside with Keith Hollis, working on rhodium and iridium carbene complexes with catalytic activity in hydroamination and hydrosilylation reactions. In 2005 he joined Illinois Wesleyan University for one year as a Visiting Assistant Professor. In 2006 he joined the University of Missouri -St. Louis as an Assistant Professor, and became promoted to Associate Professor in 2012. His research interests are the synthesis and characterization of ruthenium and iron complexes to be employed in catalytic processes. His work on ruthenium mainly concerns the catalytic activation of propargylic alcohols and their derivatives toward nucleophilic substitution reactions. In the area of iron catalysis, he published a number of iron complexes to be catalytically active in the oxidation of hydrocarbons and alcohols.

show abstract

Section: Cross Dehydrogenative Coupling Reactionsmentioning

confidence: 99%

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Bauer

2017

Israel Journal of Chemistry

View full text Add to dashboard Cite

show abstract

“…CNor . CH 2 CN radicals, either via metals such as Cu/Ag, Cu, Mn, Fe, Pt/TiO 2, or via some metal‐free radical generators such as TBPB . Similarly generation of CN − anion was achieved using various systems such as Cu, NaH .…”

Section: Reaction Solvents As Precursors For the Installation Of Key mentioning

confidence: 99%

“…The generation of . CH 2 CN radical was observed for the iron catalysed dehydrogenative sp 3 ‐sp 2 coupling of ACN and 2‐arylimidazo[1,2‐ α ]pyridine in the cyanomethylation reaction (Scheme ) . The reaction initiated with the reduction of DCP (dicumyl peroxide, 252 ) with FeCp 2 catalyst (iron‐ferrocene complex) to generate complex 253 and cumyloxyl radical, which abstracts a hydrogen atom from ACN to gave the .…”

Section: Reaction Solvents As Precursors For the Installation Of Key mentioning

confidence: 99%

Reaction Medium as the Installing Reservoir for Key Functionalities in the Molecules

2019

View full text Add to dashboard Cite

The solvent is an important entity in a chemical reaction, generally, required for the effective collision of the reactant molecules. By looking at the chemical nature, physic-chemical properties, and more importantly, smart selection, reaction solvents attract synthetic chemists for their effective use as reagents in a chemical reaction. For the installation of small key functionalities in the molecules, reaction solvents provide attractive, atom-economical, greener, and also less costly alternatives to other reagent-based strategies. For instance, particular reaction solvents can serve as a multipurpose building block for various units, such as O,

show abstract

“…239 2-Arylimidazo[1,2-a]pyridines have also been coupled with acetonitrile employing ferrocene as the catalyst and dicumyl peroxide as an oxidant (Scheme 48). 240 The proposed mechanism assumes attack of the heterocycle by a cyanomethyl radical, followed by hydrogen abstraction resulting in rearomatization. 240 Another route for the cyanomethylation of this heterocycle employed bromoacetonitrile and photocatalysis.…”

Section: Cyanomethylation Of Heteroarenesmentioning

confidence: 99%

Acetonitrile as a Building Block and Reactant

Hoff

2018

Synthesis

View full text Add to dashboard Cite

Acetonitrile is popular as a solvent for performing organic reactions, as a ligand in inorganic chemistry, as a mobile phase in chromatography, and as an electrolyte solvent in dye-sensitized solar cells. This is mainly due to its ability to dissolve both polar and nonpolar components. However, acetonitrile is also a valuable building block allowing atom-efficient transformations in synthetic organic chemistry. The aim of this review is to highlight synthetic transformations using acetonitrile, covering both classical approaches and modern strategies proceeding through radical intermediates or mediated by metal catalysis. Besides showcasing synthetic protocols useful for acetonitrile and analogues, warnings for when not to use acetonitrile as a solvent are also provided.1 Introduction2 Fundamental Reactions with Acetonitrile3 Cyanomethylation of Non-Aromatics4 The Acetonitrile Nitrogen as a Nucleophile5 The Blaise Reaction6 Synthesis of Pyridines7 Other Cyclization Reactions8 Cyanomethylation of Arenes and Heteroarenes9 Acetylation of Arenes Using Acetonitrile10 Synthesis of N-Arylacetamides11 Cyanation Using Acetonitrile as a Cyanide Source12 When To Avoid Acetonitrile as a Solvent13 Conclusion

show abstract

Iron-Catalyzed Dehydrogenative sp³–sp² Coupling via Direct Oxidative C–H Activation of Acetonitrile

Cited by 92 publications

References 74 publications

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Reaction Medium as the Installing Reservoir for Key Functionalities in the Molecules

Acetonitrile as a Building Block and Reactant

Contact Info

Product

Resources

About

Iron-Catalyzed Dehydrogenative sp3–sp2 Coupling via Direct Oxidative C–H Activation of Acetonitrile

Cited by 92 publications

References 74 publications

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Reaction Medium as the Installing Reservoir for Key Functionalities in the Molecules

Acetonitrile as a Building Block and Reactant

Contact Info

Product

Resources

About

Iron-Catalyzed Dehydrogenative sp³–sp² Coupling via Direct Oxidative C–H Activation of Acetonitrile