Selective activation of 1,2-dichloroethane for access to β-chloroethylarenes enabled by nickel-catalyzed suzuki-type couplings

• Published in: Tetrahedron letters Vol. 60; no. 16; pp. 1130 - 1134
• Main Authors: Yang, Yi, Cai, Junjie, Luo, Gen, Tong, Xia, Su, Yumei, Jiang, Yan, Liu, Yingle, Zheng, Yubin, Zeng, Jijiao, Li, Chaolin
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 18.04.2019; Elsevier
• Subjects: Chemistry; Chemistry, Organic; Chloroethylation; Combined ligands; Nickel; Physical Sciences; Science & Technology; Suzuki coupling; Suzuki coupling; Combined ligands; Chloroethylation; Nickel; TRANSITION-METAL CATALYSIS; ELIMINATION REACTIONS; CHLORIDE ELIMINATION; BOND-FORMING REACTIONS; ELECTROPHILIC DISPLACEMENT-REACTIONS; NUCLEOPHILIC-SUBSTITUTION REACTIONS; ARYLBORONIC ACIDS; UNACTIVATED ALKYL-HALIDES; BORONIC ACIDS; CROSS-COUPLINGS
• ISSN: 0040-4039; 1873-3581
• DOI: 10.1016/j.tetlet.2019.03.040

[Display omitted] •Nickel catalyzed Suzuki-type alkylation utilizing combined ligand systems.•Selective activation of one C–Cl bond of inert 1,2-dichloroethane (DCE).•Circumvent undesirable Ni-mediated β-chloride or β-hydride eliminations.•Facile access to homobenzylic chlorides in step-simplicities. The selective conversion of one inactive C(sp3)-Cl bond of 1,2-dichloroethane (DCE) into C(sp3)-C(sp2) linkages for access to β-chloroethylarenes is presented here. The key to achieve the required reactivity and chemoselectivity in this synthetic method was the utilization of nickel and combinatorial nitrogen ligands as catalytic system. Synthetic advantages of this coupling chemistry included the step-simplicities to β-chloroethylarenes, the mildness and effectiveness of coupling conditions, together with the convenience for allowing further functional group transformations of the retained homobenzylic C–Cl bonds.