Search

In the presence of a nickel catalyst, 1,3-butadiene undergoes selective dimerization and alkylarylation with alkyl fluorides and aryl Grignard reagents to give 1,6-octadienes with alkyl and aryl groups at the 3- and 8-positions, respectively, by the consecutive formation of three carbon-carbon bonds. The formation of an anionic nickel complex plays an important role in forming C−C bonds with alkyl fluorides. [ABSTRACT FROM AUTHOR]

Synthetic methods: The Ni‐catalyzed alkylation of 2‐(methylthio)benzothiazoles through CS bond cleavage is reported. Reactions with various secondary alkyl nucleophiles proceeded efficiently in the presence of 1,3‐butadiene as an additive. This reaction was proposed to proceed by σ‐bond metathesis between the thioether and a bis(π‐allyl)nickel complex or by an addition/elimination mechanism involving the CN double bond of the benzothiazoles (see scheme). [ABSTRACT FROM AUTHOR]

Starke C‐F‐Bindungen wurden mit einem anionischen Nickelkatalysator durchtrennt, um die Alkylketten der Alkylfluoride in die gewünschten Kupplungsprodukte einzubauen. In der Zuschrift auf S. 5640 ff. beschreiben N. Kambe, T. Iwasaki et al. eine nickelkatalysierte regio‐ und stereoselektive Mehrkomponentenreaktion von Alkylfluoriden, Aryl‐Grignard‐Reagentien und zwei Molekülen 1,3‐Butadien, die durch die besondere Reaktivität anionischer Bis(allyl)nickel‐Komplexe gegenüber C‐F‐Bindungen ermöglicht wird. [ABSTRACT FROM AUTHOR]

An anionic Ni complex was isolated and its structure determined by X-ray crystallography. With such an anionic complex as a key intermediate, a regio- and stereoselective multicomponent coupling reaction of perfluoroarenes, aryl Grignard reagents, and 1,3-butadiene in a 1:1:2 ratio was achieved, resulting in the formation of 1,6-octadiene derivatives containing two aryl groups, one from the perfluoroarene and the other from the aryl Grignard reagent, at the 3- and 8-positions, respectively.

In the presence of a nickel catalyst, 1,3-butadiene undergoes selective dimerization and alkylarylation with alkyl fluorides and aryl Grignard reagents to give 1,6-octadienes with alkyl and aryl groups at the 3- and 8-positions, respectively, by the consecutive formation of three carbon-carbon bonds. The formation of an anionic nickel complex plays an important role in forming C-C bonds with alkyl fluorides., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)