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1.4.8.1 Hydroarylation of Alkenes

DOI: 10.1055/sos-SD-223-00229

Nakao, Y.Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (20161425.

Bis[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]nickel(0) [Ni(IPr)2] mediates the hydroarylation of unactivated alkenes. Whereas the addition reaction of benzene remains a stoichiometric transformation, trifluoromethyl-substituted benzenes undergo a nickel-catalyzed transformation with unactivated alk-1-enes 1 with exclusive linear selectivity to give products 2 (Scheme 1).[‌1‌] The mechanism of the hydroarylation, based on theoretical calculations, involves initial formation of a bis(alkene)nickel(0) complex, which undergoes ligand exchange with an arene substrate to form an (alkene)(arene)nickel(0) species having σ-coordination of the reacting aryl—H bond (Scheme 2). Cleavage of the aryl—H bond and formation of two C—Ni bonds, as well as a newly formed C—H bond, all proceed in a concerted manner (ligand-to-ligand hydrogen transfer) to give an alkyl(aryl)nickel(II) complex, which gives an alkylated arene product after geometrical isomerization as a turnover-limiting step, followed by C—C bond forming reductive elimination.

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References


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