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Updated: Jul 12, 2026

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
Identification of an activated catalyst in the iridium-catalyzed allylic amination and etherification. Increased
Christoph A Kiener1, Chutian Shu, Christopher Incarvito
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107, USA.
Abstract:
Studies were conducted to determine possible intermediates in the highly enantioselective, iridium-catalyzed amination and etherification of allylic carbonates, and these studies revealed that cyclometalation of the phosphoramidite ligand is likely to generate the active catalyst. The square-planar [Ir(COD)(L1)Cl] (L1 = P(BINOL)(bisphenethylamine)) did not react with cinnamyl carbonate, but did react with amine to generate an Ir(I) trigonal bipyramidal complex coordinated by COD, a cyclometalated kappa2-phosphoramidite, and a kappa1-phosphoramidite. This complex reacted with phosphines to generate products from replacement of the kappa1-phosphoramidite. These cyclometalated complexes were highly active catalysts for allylic amination and etherification and retained the high selectivity of the original catalyst system. In addition, these complexes combined with [Ir(cod)Cl]2 catalyzed reactions of amines with lower loadings, catalyzed reactions of alkylamines and aromatic amines that did not react with the original catalyst system, and catalyzed reactions of phenoxides under milder conditions.
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