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1.4.2.3.4 Nickel Catalysis in Hetarylzinc Cross-Coupling Reactions

DOI: 10.1055/sos-SD-207-00504

Undheim, K.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20131759.

In a more recent report on nickel-catalyzed cross coupling, the emphasis has been on sulfanyl displacements in N-heterocyclic systems with concurrent C—C bond formation. Thus azines and azoles carrying a methylsulfanyl substituent at an electrophilic ring position undergo nickel-catalyzed cross-coupling reactions at 25 °C with functionalized hetaryl- as well as aryl- and alkylzinc reagents using the inexpensive nickel(II) acetylacetonate (1 mol%)/bis[2-(diphenylphosphino)phenyl] ether (DPEphos, 2 mol%) catalytic system (for palladium-catalyzed coupling involving methylsulfanyl-substituted hetarenes see Scheme 34, Section 1.4.2.3.3). A priori, such reactions would be expected because sulfanyl functions at electrophilic heterocyclic positions are well known to undergo nucleophilic displacements with heteroatom nucleophiles. On the other hand, sulfide substitution reactions by cross coupling in the benzenoid positions may be more difficult to perform. The nickel-catalyzed cross coupling proceeds at room temperature with high yields of the Negishi products.[‌48‌] 2-(Methylsulfanyl)pyrimidine 113 and 2-(methylsulfanyl)triazine 115 are the electrophilic substrates in the couplings illustrated in Scheme 35 and give the cross-coupled products 114 and 116, respectively.

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References


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