28593-16-0

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• 544-10-5 1-Chlorohexane 
• 352-13-6 4-flourophenylmagnesium bromide 
• 638-45-9 1-Iodohexane 
• 352-34-1 4-fluoro-1-iodobenzene 

Relevant academic research and scientific papers

Relevance of Single-Transmetalated Resting States in Iron-Mediated Cross-Couplings: Unexpected Role of σ-Donating Additives

Control of the transmetalation degree of organoiron(II) species is a critical parameter in numerous Fe-catalyzed cross-couplings to ensure the success of the process. In this report, we however demonstrate that the selective formation of a monotransmetalated FeII species during the catalytic regime counterintuitively does not alone ensure an efficient suppression of the nucleophile homocoupling side reaction. It is conversely shown that a fine control of the transmetalation degree of the transient FeIII intermediates obtained after the activation of alkyl electrophiles by a single-electron transfer (SET), achievable using σ-donating additives, accounts for the selectivity of the cross-coupling pathway. This report shows for the first time that both coordination spheres of FeII resting states and FeIII short-lived intermediates must be efficiently tuned during the catalytic regime to ensure high coupling selectivities.

Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMeImd-BH3

The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH3) are reported. These reactions proceed via a radical mechanism that involves the addition of a borane radical to the nitrile to form an iminyl radical, followed by cleavage of a carbon-carbon bond. Theoretical calculations suggest that the β-cleavage of these iminyl radicals, which affords NHC-BH2CN and the corresponding alkyl radicals, is the rate-determining step in this reaction.

Silver-mediated fluorination of potassium aryltrifluoroborates with Selectfluor Dedicated to Professor Andrea Vasella on the occasion of his 71st birthday

A simple and practical procedure for the silver-mediated fluorination of aryl- and heteroaryltrifluoroborates with electrophilic fluorine from Selectfluor and LiOH·H2O is presented. The reaction procedure is simple and easy to set up, the process produces fluorinated arenes and heteroarenes in good to excellent yields and a wide range of electronically and structurally diverse substrates are tolerated.

First Kumada reaction of alkyl chlorides using N-heterocyclic carbene/palladium catalyst systems

For the first time it is shown that N-heterocyclic carbenes are suitable ligands for the palladium-catalyzed coupling of alkyl chlorides with aryl Grignard reagents. A variety of simple as well as functionalized primary alkyl chlorides provide the corresponding alkyl benzenes in general in good to very good yield. By comparing the 1,3-dimesitylimidazol-2-ylidene (IMes) palladium(0) naphthoquinone complex with the previously known palladium phosphine catalyst for the model coupling reaction of 1-chlorohexane with phenylmagnesium bromide it is demonstrated that the new catalyst system is superior.

Palladium-catalyzed coupling of alkyl chlorides and Grignard reagents

Chloroalkanes refined: A simple catalyst system renders the palladium-catalyzed coupling reaction of functionalized alkyl chlorides and Grignard reagents at room temperature (see example in scheme; PCy3 = tricyclohexylphosphane, NMP = N-methylpyrrolidinone).