Functional Group Tolerant Kumada-Corriu-Tamao Coupling of Nonactivated Alkyl Halides with Aryl and Heteroaryl Nucleophiles: Catalysis by a Nickel Pincer Complex Permits the Coupling of Functionalized Grignard Reagents was written by Vechorkin, Oleg;Proust, Valerie;Hu, Xile. And the article was included in Journal of the American Chemical Society in 2009.Application In Synthesis of N,N-Diethyl-4-iodobenzamide This article mentions the following:
A nickel(II) pincer complex [(MeNN2)NiCl] (I) [MeNN2 = di(2-dimethylaminophenyl)amine] catalyzes Kumada-Corriu-Tamao cross-coupling of nonactivated alkyl halides with aryl and heteroaryl Grignard reagents. The coupling of octyl bromide with phenylmagnesium chloride was used as a test reaction. Using 3 mol % of I as the precatalyst and THF as the solvent, and in the presence of a catalytic amount of TMEDA, the coupling product was obtained in a high yield. The reaction conditions could be applied to cross coupling of other primary and secondary alkyl bromides and iodides. The coupling is tolerant to a wide range of functional groups. Therefore, alkyl halides containing ester, amide, ether, thioether, alc., pyrrole, indole, furan, nitrile, conjugated enone, and aryl halide moieties were coupled to give high isolated yields of products in which these units stay intact. For the coupling of ester-containing substrates, O-TMEDA is a better additive than TMEDA. The reaction protocol proves to be efficient for the coupling of Knochel-type functionalized Grignard reagents. Thus, aryl Grignard reagents containing electron-deficient and/or sensitive ester, nitrile, amide, and CF3 substituents could be successfully coupled to nonactivated and functionalized alkyl iodides. The catalysis is also efficient for the coupling of alkyl iodides with functionalized heteroaryl Grignard reagents, giving rise to pyridine-, thiophene-, pyrazole-, furan-containing mols. with addnl. functionalities. Concerning the mechanism of the catalysis, [(MeNN2)Ni-(hetero)Ar] was identified as an intermediate, and the activation of alkyl halides was found to take place through a radical-rebound process. In the experiment, the researchers used many compounds, for example, N,N-Diethyl-4-iodobenzamide (cas: 77350-52-8Application In Synthesis of N,N-Diethyl-4-iodobenzamide).
N,N-Diethyl-4-iodobenzamide (cas: 77350-52-8) belongs to iodide derivatives. Typical reactions of alkyl iodides include nucleophilic substitution, elimination, reduction, and the formation of organometallics. A typical method for synthesis of aromatic iodides is diazotization of primary aromatic amines followed by treatment of potassium iodide. Aliphatic alcohols are converted to alkyl iodides by treating with hydrogen iodide.Application In Synthesis of N,N-Diethyl-4-iodobenzamide
Referemce:
Iodide – Wikipedia,
Iodide – an overview | ScienceDirect Topics – ScienceDirect.com