Nickel-Catalyzed Stille Cross Coupling of C-O Electrophiles
Russell, John E.
Entz, Emily D.
Joyce, Ian M.
Neufeldt, Sharon R.
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Aryl sulfamates, tosylates, and mesylates undergo efficient Ni-catalyzed cross coupling with diverse organostannanes in the presence of relatively unhindered alkylphosphine ligands and KF. The coupling is valuable for difficult bond constructions, such as aryl-heteroaryl, aryl-alkenyl, and aryl-alkynyl, using nontriflate phenol derivatives. A combination of experimental and computational studies implicates an unusual mechanism for transmetalation involving an 8-centered cyclic transition state. This reaction is inhibited by chloride sources due to slow transmetalation of organostannanes at a Ni(II)-chloride intermediate. These studies help to explain why prior efforts to achieve Ni-catalyzed Stille coupling of phenol derivatives were unsuccessful.
Russell, John E. A., Emily D. Entz, Ian M. Joyce, and Sharon R. Neufeldt. "Nickel-Catalyzed Stille Cross Coupling of C-O Electrophiles." ACS Catalysis 9, no. 4 (April 2019): 3304-3310. DOI:10.1021/acscatal.9b00744.