Anti-Markovnikov N−H and O−H Additions to Electron-Deficient Olefins Catalyzed by Well-Defined Cu(I) Anilido, Ethoxide, and Phenoxide Systems
- 12 January 2006
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (5) , 1446-1447
- https://doi.org/10.1021/ja057622a
Abstract
The monomeric Cu(I) complexes (IPr)Cu(Z) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, Z = NHPh, OEt, or OPh) react with YH (Y = PhNH, PhCH2NH, EtO, or PhO) to catalytically add Y-H bonds across the C=C bond of electron-deficient olefins to yield anti-Markovnikov organic products. Catalytic activity has been observed for olefins CH2C(H)(X) with X = CN, C(O)Me, or CO2Me as well as crotononitrile. Preliminary studies implicate an intermediate in which the C-Y bond forms through a nucleophilic addition pathway.Keywords
This publication has 11 references indexed in Scilit:
- Rhodium-catalyzed addition of alcohols to terminal enonesTetrahedron Letters, 2004
- Catalytic Markovnikov and anti‐Markovnikov Functionalization of Alkenes and Alkynes: Recent Developments and TrendsAngewandte Chemie International Edition in English, 2004
- LiClO4 Accelerated Michael addition of amines to α,β-unsaturated olefins under solvent-free conditionsTetrahedron, 2004
- Rhodium-Catalyzed Asymmetric 1,4-Addition and Its Related Asymmetric ReactionsChemical Reviews, 2003
- Phosphine-Catalyzed Hydration and Hydroalkoxylation of Activated Olefins: Use of a Strong Nucleophile to Generate a Strong BaseJournal of the American Chemical Society, 2003
- A General, Brønsted Acid-Catalyzed Hetero-Michael Addition of Nitrogen, Oxygen, and Sulfur NucleophilesOrganic Letters, 2003
- Kinetics and Mechanisms of Methyl Vinyl Ketone Hydroalkoxylation Catalyzed by Palladium(II) ComplexesOrganometallics, 2001
- Transition Metal-Catalyzed Addition of Amines to Acrylic Acid Derivatives. A High-Throughput Method for Evaluating Hydroamination of Primary and Secondary AlkylaminesOrganometallics, 2001
- Phosphoramidites: Marvellous Ligands in Catalytic Asymmetric Conjugate AdditionAccounts of Chemical Research, 2000
- Asymmetric conjugate additionChemical Reviews, 1992