364359-10-4Relevant academic research and scientific papers
Efficient synthesis of functionalized organozinc compounds by the direct insertion of zinc into organic iodides and bromides
Krasovskiy, Arkady,Malakhov, Vladimir,Gavryushin, Andrei,Knochel, Paul
, p. 6040 - 6044 (2006)
(Chemical Equation Presented) Insider dealing: A wide range of poly-functional (hetero)aromatic and aliphatic zinc reagents can be easily prepared in THF. The compounds are formed by a Zn insertion reaction mediated by the addition of LiCl (see scheme; All = allyl).
Replacing conventional carbon nucleophiles with electrophiles: Nickel-catalyzed reductive alkylation of aryl bromides and chlorides
Everson, Daniel A.,Jones, Brittany A.,Weix, Daniel J.
supporting information; experimental part, p. 6146 - 6159 (2012/05/07)
A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO2Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe3), and organosilicon (-SiMe2OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents.
Copper-mediated cross-coupling of functionalized arylmagnesium reagents with functionalized alkyl and benzylic halides
Dohle, Wolfgang,Lindsay, David M.,Knochel, Paul
, p. 2871 - 2873 (2007/10/03)
(equation presented) Functionalized arylmagnesium halides, prepared via an iodine-magnesium exchange, undergo a smooth cross-coupling reaction with functionalized primary alkyl iodides and benzylic bromides in the presence of CuCN·2LiCl, either in stoichi
