Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation.

Autor: Dürr AB; Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany., Fisher HC; Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany., Kalvet I; Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany., Truong KN; Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany., Schoenebeck F; Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2017 Oct 16; Vol. 56 (43), pp. 13431-13435. Date of Electronic Publication: 2017 Sep 14.
DOI: 10.1002/anie.201706423
Abstrakt: We herein showcase the ability of NHC-coordinated dinuclear Ni I -Ni I complexes to override fundamental reactivity limits of mononuclear (NHC)Ni 0 catalysts in cross-couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a Ni I dimer. A novel SeCF 3 -bridged Ni I dimer was isolated and shown to selectively react with Ar-I bonds. Our computational and experimental reactivity data suggest dinuclear Ni I catalysis to be operative. The corresponding Ni 0 species, on the other hand, suffers from preferred reaction with the product, ArSeCF 3 , over productive cross-coupling and is hence inactive.
(© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)
Databáze: MEDLINE
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