Silanes in organic synthesis. 15. Silicon-directed hydride abstraction from [2-(trimethylsilyl)-1,3-cyclohexadiene]iron tricarbonyl complexes and nucleophilic addition to the derived cations

1982 ◽  
Vol 1 (5) ◽  
pp. 757-760 ◽  
Author(s):  
Leo A. Paquette ◽  
Rhys G. Daniels
Keyword(s):  
Organic Synthesis ◽  
Nucleophilic Addition ◽  
Hydride Abstraction ◽  
Iron Tricarbonyl

scholarly journals Iron-Catalyzed C(sp2)–C(sp3) Cross-Coupling of Aryl Chlorobenzoates with Alkyl Grignard Reagents

Molecules ◽  
2020 ◽  
Vol 25 (1) ◽  
pp. 230 ◽  
Author(s):  
Elwira Bisz ◽  
Michal Szostak
Keyword(s):  
Organic Synthesis ◽  
Nucleophilic Addition ◽  
Functional Group ◽  
High Selectivity ◽  
Cross Coupling ◽  
Environmentally Benign ◽  
Grignard Reagents ◽  
High Importance ◽  
Iron Salts ◽  
The Cross

Aryl benzoates are compounds of high importance in organic synthesis. Herein, we report the iron-catalyzed C(sp2)–C(sp3) Kumada cross-coupling of aryl chlorobenzoates with alkyl Grignard reagents. The method is characterized by the use of environmentally benign and sustainable iron salts for cross-coupling in the catalytic system, employing benign urea ligands in the place of reprotoxic NMP (NMP = N-methyl-2-pyrrolidone). It is notable that high selectivity for the cross-coupling is achieved in the presence of hydrolytically-labile and prone to nucleophilic addition phenolic ester C(acyl)–O bonds. The reaction provides access to alkyl-functionalized aryl benzoates. The examination of various O-coordinating ligands demonstrates the high activity of urea ligands in promoting the cross-coupling versus nucleophilic addition to the ester C(acyl)–O bond. The method showcases the functional group tolerance of iron-catalyzed Kumada cross-couplings.

1,2-Disubstituted [(η6-Arene)Cr(CO)3] Complexes by Sequential Nucleophilic Addition/endo-Hydride Abstraction

1998 ◽  
Vol 4 (2) ◽  
pp. 251-259 ◽  
Author(s):  
Angelika Fretzen ◽  
Alberto Ripa ◽  
Ronggang Liu ◽  
Gerald Bernardinelli ◽  
E. Peter Kündig
Keyword(s):  
Nucleophilic Addition ◽  
Hydride Abstraction

ChemInform Abstract: 1,2-Disubstituted [(η6-Arene)Cr(CO)3] Complexes by Sequential Nucleophilic Addition/endo-Hydride Abstraction.

ChemInform ◽  
2010 ◽  
Vol 29 (23) ◽  
pp. no-no
Author(s):  
A. FRETZEN ◽  
A. RIPA ◽  
R. LIU ◽  
G. BERNARDINELLI ◽  
E. P. KUENDIG
Keyword(s):  
Nucleophilic Addition ◽  
Hydride Abstraction

Reactivity of heterodiene metal carbonyl complexes

1988 ◽  
Vol 326 (1592) ◽  
pp. 611-617 ◽  
Keyword(s):  
Nucleophilic Addition ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
Unsaturated Esters ◽  
Unsaturated Ketones ◽  
Metal Carbonyl Complexes ◽  
Unsaturated Amine ◽  
Iron Tricarbonyl

Addition of hard nucleophiles to iron tricarbonyl complexes of α,β-unsaturated ketones and iron tetracarbonyl complexes of α,β-unsaturated esters produces γ-ketocarbonyl compounds. Nucleophilic addition to iron tricarbonyl complexes of α,β-unsaturated imines leads either to pyrrole or α,β-unsaturated amine formation

scholarly journals Photocatalytic α-Alkylation of Amines with Alkyl Halides

2020 ◽  
Author(s):  
Lingying Leng ◽  
Joseph Ready
Keyword(s):  
Organic Synthesis ◽  
Nucleophilic Addition ◽  
Building Blocks ◽  
Alkyl Halides ◽  
Organometallic Reagents ◽  
Dehydrogenative Coupling ◽  
Alkyl Bromides ◽  
Alternative Approach ◽  
Traditionally Prepared ◽  
Carbon Centered Radical

a-Branched amines represent essential building blocks for organic synthesis. They are traditionally prepared through nucleophilic addition to imines. These methods often require highly reactive organometallic reagents and proceed under rigorous air- and moisture-free conditions. Here we describe an alternative approach that involves a net dehydrogenative coupling between alkyl bromides and amines. Mechanistically, the reaction likely involves photocatalytic generation of an a-amino radical and a stabilized carbon-centered radical (allyl, benzyl, a-carbonyl) followed by radical recombination. This approach offers a mild, atom-economical, redox neutral synthesis of a-branched amines that shows broad scope and avoids pre-metalated reagents.

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