Easy Routes towards Chiral Lithium Binaphthylamido Catalysts for the Asymmetric Hydroamination of Amino‐1,3‐dienes and Aminoalkenes
- 9 May 2011
- journal article
- research article
- Published by Wiley in European Journal of Organic Chemistry
- Vol. 2011 (18) , 3329-3338
Abstract
The preparation of chiral lithium salts of N,N′‐disubstituted binaphthyldiamines and their use as catalysts for asymmetric hydroamination/cyclisation of amino‐1,3‐dienes and aminoalkenes are reported. Several straightforward methods involving the combination of ligand with solutions of methyl‐ or [(trimethylsilyl)methyl]lithium (LiCH2TMS) by ex situ or in situ preparation have been investigated. The use of LiCH2TMS in an in situ procedure was revealed as theeasiest for carrying out reactions with reliable results by fine‐tuning the quantity of base. Screening of a variety of ligands led to the selection of binaphthyldiamines modified by benzyl, pyridyl or naphthyl groups for the cyclisation of conjugated aminodienes in pyrrolidine or piperidine with the highest stereo‐ and enantioselectivities described to date (up to 61 and 72 % ee, respectively). Primary and secondaryaminoalkenes are efficiently cyclised at room temperature, but with poor enantioselectivities.Keywords
This publication has 103 references indexed in Scilit:
- Platinum(ii)-catalyzed intermolecular hydroamination of monosubstituted allenes with secondary alkylaminesChemical Communications, 2010
- The enantioselective intramolecular aminative functionalization of unactivated alkenes, dienes, allenes and alkynes for the synthesis of chiral nitrogen heterocyclesOrganic & Biomolecular Chemistry, 2009
- Intermolecular Hydroamination of Ethylene and 1-Alkenes with Cyclic Ureas Catalyzed by Achiral and Chiral Gold(I) ComplexesJournal of the American Chemical Society, 2009
- Convenient method for the rapid generation of highly active and enantioselective yttrium catalysts for asymmetric hydroaminationChemical Communications, 2008
- Mild, Rhodium-Catalyzed Intramolecular Hydroamination of Unactivated Terminal and Internal Alkenes with Primary and Secondary AminesJournal of the American Chemical Society, 2008
- Structure−Activity Relationships for Group 4 Biaryl Amidate Complexes in Catalytic Hydroamination/Cyclization of AminoalkenesOrganometallics, 2007
- Zirconium Bis(Amido) Catalysts for Asymmetric Intramolecular Alkene HydroaminationOrganometallics, 2006
- Optically Active Transition-Metal Complexes. 10.1 Bifunctional Arene−Chromium−Tricarbonyl Complexes Derived from (R)-Phenylethanamine: Easily Accessible Planar-Chiral Diphosphines and Their Application in Enantioselective Hydrogenation, Hydroamination, and Allylic SulfonationOrganometallics, 2000
- Unsaturated Aromatic Amines; a Novel Synthesis of IndolesJournal of the American Chemical Society, 1958
- Alkali Metal-catalyzed Amination of OlefinsJournal of the American Chemical Society, 1954