Selective C−H Activation α to Primary Amines. Bridging Metallaaziridines for Catalytic, Intramolecular α-Alkylation
Authors:
- 27 January 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 131 (6) , 2116-2118
Abstract
Selective α-C−H activation results in the synthesis of the first bridging metallaaziridine complex for the catalytic α-alkylation of primary amines. Reaction development led to the preparation of new Zr 2-pyridonate complexes for this useful transformation. No nitrogen protecting groups are required for this reaction, which is capable of assembling quaternary chiral centers α to nitrogen. Preliminary mechanistic investigations suggest bridging metallaaziridine species are the catalytically active intermediates for this α-functionalization reaction, while monomeric imido complexes furnish azepane hydroamination products.Keywords
This publication has 25 references indexed in Scilit:
- Titanium‐Catalyzed Hydroaminoalkylation of Alkenes by C-H Bond Activation at sp3 Centers in the α‐Position to a Nitrogen AtomAngewandte Chemie International Edition, 2009
- Hydroaminoalkylation of Unactivated Olefins with DialkylaminesJournal of the American Chemical Society, 2008
- Hydroamination: Direct Addition of Amines to Alkenes and AlkynesChemical Reviews, 2008
- Neutral Group‐IV Metal Catalysts for the Intramolecular Hydroamination of AlkenesEuropean Journal of Organic Chemistry, 2008
- Direct, Catalytic Hydroaminoalkylation of Unactivated Olefins with N-Alkyl ArylaminesJournal of the American Chemical Society, 2007
- Enantiomerically Pure Amines as Substrates for the Ti‐Catalyzed Hydroamination of AlkynesEuropean Journal of Organic Chemistry, 2004
- Microwave-Assisted Catalytic Intermolecular Hydroamination of AlkynesEuropean Journal of Organic Chemistry, 2001
- Structure-reactivity correlations for the formation of zirconocene .eta.2-imine complexes from aminesOrganometallics, 1994
- Zirconocene complexes of imines. General synthesis, structure, reactivity, and in situ generation to prepare geometrically pure allylic aminesJournal of the American Chemical Society, 1989
- Catalytic C-H activation in early transition-metal dialkylamides and alkoxidesOrganometallics, 1983