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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Oxidatively Triggered Carbon-Carbon Bond Formation in Ene-amide Complexes
Brian P Jacobs1, Peter T Wolczanski1, Emil B Lobkovsky1
1Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853, United States.
Inorganic Chemistry
|April 12, 2016
Summary
This study explores oxidative coupling of ene-amides using chromium, iron, and cobalt complexes. These metal complexes facilitate C-C bond formation and C-arylation reactions, offering new synthetic pathways.
Area of Science:
- Organometallic Chemistry
- Synthetic Organic Chemistry
Background:
- Ene-amides are versatile organic compounds with potential applications as ligands and substrates.
- Oxidative coupling reactions are crucial for forming carbon-carbon bonds in organic synthesis.
Purpose of the Study:
- To investigate the synthesis and reactivity of metal-ene-amide complexes.
- To explore the use of these complexes in oxidative coupling and C-arylation reactions.
Main Methods:
- Treatment of various metal chlorides (CrCl2, Cl2Fe(PMe3)2, Cl2Copy4) with lithium ene-amides.
- Oxidative triggering of C-C bond formation using CrCl3 and FeCl3.
- Catalytic C-arylation reactions with ferrous compounds and phenyl bromide.
- Structural characterization of synthesized metal complexes.
Main Results:
- Synthesis of novel chromium, iron, and cobalt ene-amide complexes in high yields.
- Successful oxidative coupling leading to C-C bond formation (rac-2,2'-di(2,6-(i)Pr2C6H3N═)2dicyclohexane).
- Demonstration of ferrous-catalyzed C-arylation of lithium ene-amides with phenyl bromide, albeit with variability.
- Structural elucidation of key metal complexes.
Conclusions:
- Metal-ene-amide complexes serve as effective platforms for oxidative coupling and C-C bond formation.
- Ferrous compounds show catalytic activity in C-arylation, indicating potential for further development.
- The study provides insights into the reactivity and synthetic utility of ene-amides in organometallic chemistry.
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