Details

Autor(en) / Beteiligte

• Haibach, Michael C
• Ickes, Andrew R
• Tcyrulnikov, Sergei
• Shekhar, Shashank
• Monfette, Sebastien
• Swiatowiec, Rafal
• Kotecki, Brian J
• Wang, Jason
• Wall, Amanda L
• Henry, Rodger F
• Hansen, Eric C

Titel

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

Ist Teil von

• Chemical science (Cambridge), 2022-11, Vol.13 (43), p.1296-12912

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2022

Quelle

Free E-Journal (出版社公開部分のみ）

Beschreibungen/Notizen

• 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 2 Me) 2 NiCl 2 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 K 3 PO 4 ) 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 PPh 2 Me 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. A simple inexpensive ligand enables the Ni-catalyzed Suzuki-Miyaura coupling of heterocyclic and Lewis-basic arylboronic esters under mild conditions.