A nickel-catalyzed reductive cross-electrophile coupling between the redox-active N-trifluoroeth-oxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2-Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α-hydroxy-α-trifluoromethyl C-centered radical for theC sp2Csp3 bond forming process.
Direct Synthesis of α-Aryl-α-Trifluoromethyl Alcohols via Nickel Catalyzed Cross-Electrophile Coupling / Lombardi, Lorenzo; Cerveri, Alessandro; Giovanelli, Riccardo; Castiñeira Reis, Marta; Silva López, Carlos; Bertuzzi, Giulio; Bandini, Marco. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 61:47(2022), pp. e202211732.1-e202211732.6. [10.1002/anie.202211732]
Direct Synthesis of α-Aryl-α-Trifluoromethyl Alcohols via Nickel Catalyzed Cross-Electrophile Coupling
Alessandro Cerveri;
2022-01-01
Abstract
A nickel-catalyzed reductive cross-electrophile coupling between the redox-active N-trifluoroeth-oxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2-Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α-hydroxy-α-trifluoromethyl C-centered radical for theC sp2Csp3 bond forming process.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
