139597-68-5Relevant articles and documents
Nickel-Catalyzed Kumada Coupling of Benzyl Chlorides and Vinylogous Derivatives
Soler-Yanes, Rita,Guisán-Ceinos, Manuel,Bu?uel, Elena,Cárdenas, Diego J.
, p. 6625 - 6629 (2014)
Conditions for the fast Ni-catalyzed Kumada-type cross-coupling of functionalized benzyl and allyl chlorides with alkylmagnesium reagents were discovered. The use of Ni(acac)2-TMEDA (acac = acetylacetonate, TMEDA = N,N,N′,N′-tetramethyl-1,2-ethylenediamine) allows the presence of reactive functional groups on the electrophile. On the other hand, the use of diallyl ether was shown to provide fast coupling at low temperature with a low catalyst loading. The reaction seems to follow a radical pathway.
Metal-Reductant-Free Electrochemical Nickel-Catalyzed Couplings of Aryl and Alkyl Bromides in Acetonitrile
Perkins, Robert J.,Hughes, Alexander J.,Weix, Daniel J.,Hansen, Eric C.
supporting information, p. 1746 - 1751 (2019/08/20)
While reductive cross-electrochemical coupling is an attractive approach for the synthesis of complex molecules at both small and large scale, two barriers for large-scale applications have remained: the use of stoichiometric metal reductants and a need for amide solvents. In this communication, new conditions that address these challenges are reported. The nickel-catalyzed reductive cross-coupling of aryl bromides with alkyl bromides can be conducted in a divided electrochemical cell using acetonitrile as the solvent and diisopropylamine as the sacrificial reductant to afford coupling products in synthetically useful yields (22-80%). Additionally, the use of a combination of the ligands 4,4′,4″-tri-tert-butyl-2,2′:6′,2′-terpyridine and 4,4′-di-tert-butyl-2,2′-bipyridine is essential to achieve high yields.
Mechanochemical Activation of Zinc and Application to Negishi Cross-Coupling
Cao, Qun,Howard, Joseph L.,Wheatley, Emilie,Browne, Duncan L.
, p. 11339 - 11343 (2018/08/28)
A form independent activation of zinc, concomitant generation of organozinc species and engagement in a Negishi cross-coupling reaction via mechanochemical methods is reported. The reported method exhibits a broad substrate scope for both C(sp3)–C(sp2) and C(sp2)–C(sp2) couplings and is tolerant to many important functional groups. The method may offer broad reaching opportunities for the in situ generation organometallic compounds from base metals and their concomitant engagement in synthetic reactions via mechanochemical methods.
