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Enabling Suzuki-Miyaura coupling of Lewis-basic arylboronic esters with a nonprecious metal catalyst.

ABSTRACT: The high cost and negative environmental impact of precious metal catalysts has led to increased demand for nonprecious alternatives for widely practiced reactions such as the Suzuki-Miyaura coupling (SMC). Ni-catalyzed versions of this reaction have failed to achieve high reactivity with Lewis-basic arylboron nucleophiles, especially pinacolboron esters. We describe the development of (PPh2Me)2NiCl2 as an inexpensive and air-stable precatalyst that addresses this challenge. Under activation by n-BuMgCl, this complex can catalyze the coupling of synthetically important heteroaryl pinacolborons with heteroaryl halides. Mildly basic conditions (aqueous K3PO4) allow the reaction to tolerate sensitive functional groups that were incompatible with other Ni-SMC methods. Experimental and computational studies suggest that catalyst inhibition by substitution of PPh2Me from Ni(ii) intermediates by Lewis basic reactants and products is disfavored relative to more commonly employed ligands in the Ni-SMC, which allows it to operate efficiently in the presence of Lewis bases such as unhindered pyridines.

SUBMITTER: Haibach MC 

PROVIDER: S-EPMC9645418 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Enabling Suzuki-Miyaura coupling of Lewis-basic arylboronic esters with a nonprecious metal catalyst.

Haibach Michael C MC   Ickes Andrew R AR   Tcyrulnikov Sergei S   Shekhar Shashank S   Monfette Sebastien S   Swiatowiec Rafal R   Kotecki Brian J BJ   Wang Jason J   Wall Amanda L AL   Henry Rodger F RF   Hansen Eric C EC  

Chemical science 20221021 43

The high cost and negative environmental impact of precious metal catalysts has led to increased demand for nonprecious alternatives for widely practiced reactions such as the Suzuki-Miyaura coupling (SMC). Ni-catalyzed versions of this reaction have failed to achieve high reactivity with Lewis-basic arylboron nucleophiles, especially pinacolboron esters. We describe the development of (PPh<sub>2</sub>Me)<sub>2</sub>NiCl<sub>2</sub> as an inexpensive and air-stable precatalyst that addresses thi  ...[more]

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