1560-97-0Relevant articles and documents
Copper-catalyzed alkyl-alkyl cross-coupling reactions using hydrocarbon additives: Efficiency of catalyst and roles of additives
Iwasaki, Takanori,Imanishi, Reiko,Shimizu, Ryohei,Kuniyasu, Hitoshi,Terao, Jun,Kambe, Nobuaki
, p. 8522 - 8532 (2015/01/08)
Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h-1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu-H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu-H promotes the reduction of alkyl halides to give alkanes and Cu-X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.
Cobalt-catalyzed cross-coupling reaction between functionalized primary and secondary alkyl halides and aliphatic Grignard reagents
Cahiez, Gerard,Chaboche, Christophe,Duplais, Christophe,Giulliani, Arianna,Moyeux, Alban
supporting information; experimental part, p. 1484 - 1488 (2009/07/01)
The coupling of primary and secondary unactivated alkyl bromides with alkyl-Grignard reagents was performed in good yields under mild conditions by using a new catalytic system: consisting of cobalt chloride and tetramethylethylenediamine (CoCl2·2 LiI, 4TMEDA). The reaction is very chemoselective since ketone, ester and nitrile functions are tolerated.
Copper-catalyzed cross-coupling reaction of Grignard reagents with primary-alkyl halides: Remarkable effect of 1-phenylpropyne
Terao, Jun,Todo, Hirohisa,Begum, Shameem Ara,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 2086 - 2089 (2008/02/14)
(Chemical Equation Presented) A general get-together: The Cu-catalyzed cross-coupling reaction of primary-alkyl halides with primary-, secondary-, and tertiary-alkyl and phenyl Grignard reagents proceeds efficiently in THF under reflux in the presence of 1-phenylpropyne (see scheme). The reaction is also applicable to alkyl mesylates (OMs) and tosylates (OTs). The reactivities of alkyl-X with a Grignard reagent increase in the order X = Cl F OMs OTs Br.
