548459-52-5Relevant academic research and scientific papers
Copper-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Alkyl Fluorides and Grignard Reagents
Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 9347 - 9350 (2015)
Copper complexes generated in situ from CuCl2, alkyl Grignard reagents, and 1,3-dienes play important roles as catalytic active species for the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides through C-F bond cleavage. The alkyl group is introduced to an internal carbon atom of the 1,3-diene regioselectively, thus giving rise to the branched terminal alkene product. Making the switch: A copper-hydride species, generated by the treatment of a copper salt with alkyl Grignard reagents, catalyzes the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides and Grignard reagents. The alkyl group of the alkyl fluoride is selectively introduced to an internal carbon atom of the 1,3-diene and the Grignard reagent acts as hydride source to give the branched terminal alkene, even in the presence of alkenes and alkynes.
Nickel-Catalyzed Dimerization and Alkylarylation of 1,3-Dienes with Alkyl Fluorides and Aryl Grignard Reagents
Iwasaki, Takanori,Min, Xin,Fukuoka, Asuka,Kuniyasu, Hitoshi,Kambe, Nobuaki
supporting information, p. 5550 - 5554 (2016/05/09)
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.
Ni- or Cu-catalyzed cross-coupling reaction of alkyl fluorides with grignard reagents
Terao, Jun,Ikumi, Aki,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 5646 - 5647 (2007/10/03)
n-Octyl fluoride underwent a cross-coupling reaction with n-propylmagnesium bromide in the presence of 1,3-butadiene using NiCl2 as a catalyst at room temperature to give undecane in moderate yields. This alkyl-alkyl cross-coupling proceeded more efficiently when CuCl2 was employed instead of NiCl2. Addition of 1,3-butadiene dramatically improved the yields of the coupling products from primary alkyl Grignard reagents in both Ni- and Cu-catalyzed reactions. Alkyl fluorides efficiently reacted with tertiary alkyl and phenyl Grignard reagents using CuCl2 in the absence of 1,3-butadiene to afford the coupling products in high yields. The competitive reaction of a mixture of alkyl halides (R-X; X = F, Cl, Br) with nC5H11MgBr showed that the reactivities of the halides increase in the order R-Cl R-F R-Br. In contrast, in the Cu-catalyzed reaction with PhMgBr, the reactivities increase in the order R-Cl R-Br R-F. Copyright
