Halides coupling reactions with primary alkyl Grignard

While alkynyllithiums react with primary alkyl halides in the presence of diamines or HMPA to afford the coupled products [35], this reaction proceeds slowly in the absence of these additives, even at elevated temperature. Luh has described a Pd/PPh3 catalyst that facilitates the cross-coupling of alkynyllithiums and alkynyl Grignard reagents with primary alkyl bromides and iodides (e.g.,Eq.l5) [37]. 

Primary, secondary, and tertiary Grignard reagents react with primary alkyl bromides, iodides, and tosylates in a CuCl-catalysed cross-coupling 5 2 reaction. Yields range from 73 to 94%. The reaction tolerates a wide variety of substituents on the alkyl halide and alkyl or aryl groups can be used in the Grignard reagent. 

Decomposition of azo compounds and peroxides provides the alkoxyamine by the nitroxide-trapping of the primary radicals [29]. The radicals produced by hydrogen abstraction with oxy radicals are also trapped by the nitroxide [242, 243]. In the photoreaction, alkoxyamines were isolated with high yields [244]. The reactions of Grignard reagents with nitroxides [215] and the coupling reaction of sodium nitroxides with bromo compounds [234,235] are also used. The hydrolysis of 56 followed by the reaction with acyl or alkyl halides afforded alkoxyamines with various functional groups,63 (Eq. 68) [245-251] ... 

Transition metal-catalyzed cross-coupling reactions between vinyl organometallic compounds and unactivated alkyl halides that can be usually performed with palladium, nickel and cobalt are of particular synthetic interest [37-39]. Recently, the groups of Cahiez [48] and Cossy [49] concurrently reported the first iron-catalyzed reaction of alkenyl Grignard compounds with primary and secondary alkyl halides (X=Br, I) (Scheme 5.15). The two protocols basically differ in the iron source... 

Tamura and Kochi studied the cross-coupling reactions of alkyl halides with alkyl Grignard reagents catalyzed by silver compounds first [422, 426, 427]. The coupling of primary alkyl halides with primary Grignard reagents resulted in a mixture... 

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