Palladium-Catalyzed Intramolecular Asymmetric Hydroamination, Hydroalkoxylation, and Hydrocarbonation of Alkynes
- 29 April 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 71 (11) , 4270-4279
- https://doi.org/10.1021/jo0603835
Abstract
A conceptually novel approach for asymmetric intramolecular hydroamination, hydroalkoxylation and hydrocarbonation of alkynes using chiral palladium catalysts are described. The reactions of the aminoalkynes 5, alkynols 7, and alkynylmethines 9 in the presence of Pd2(dba)3·CHCl3/PhCOOH/renorphos 4 in benzene (or benzene−hexane) at 100 °C gave the corresponding cyclization products (nitrogen heterocycles 6, oxygen heterocycles 8, and carbocycles 10) in good yields with good enantioselectivities. The origins of enantioselectivities in the hydroamination reaction are discussed based on DFT computations.Keywords
This publication has 44 references indexed in Scilit:
- Pd(0)–PhCOOH catalyzed addition of oxygen pronucleophiles to allenes and internal alkynesCanadian Journal of Chemistry, 2005
- Density Functional Study of Mo-Carbonyl-Catalyzed Alkynol Cycloisomerization: Comparison with W-Catalyzed ReactionOrganometallics, 2005
- Palladium‐Catalyzed Equilibrium Addition of Acidic OH Groups across DienesAngewandte Chemie International Edition in English, 2003
- Enantioselective Catalytic Hydroamination of AlkenesAngewandte Chemie International Edition in English, 2003
- 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
- The [IrCl(Diphosphine)]2/Fluoride System. Developing Catalytic Asymmetric Olefin HydroaminationJournal of the American Chemical Society, 1997
- The accuracy of the pseudopotential approximation. II. A comparison of various core sizes for indium pseudopotentials in calculations for spectroscopic constants of InH, InF, and InClThe Journal of Chemical Physics, 1996
- The Atom Economy—A Search for Synthetic EfficiencyScience, 1991
- Capillary gas chromatographic separation of enantiomers with stable dipentyl-α, β- and γ-cyclodextrin-derivatized stationary phasesAnalytica Chimica Acta, 1990
- Palladium-catalyzed additions of amines to conjugated dienes. Alteration of behavior of triphenylphosphine-palladium catalysts with amine hydroiodide saltsOrganometallics, 1986