Chiral Phosphoric Acid Catalyzed Enantioselective Synthesis of α-Tertiary Amino Ketones from Sulfonium Ylides
- 22 July 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (33), 14384-14390
- https://doi.org/10.1021/jacs.0c07210
Abstract
Herein we disclose a new catalytic asymmetric approach for the synthesis of chiral α-amino ketones, which is particularly useful for the less accessible acyclic α-tertiary cases. By a protonation-amination sequence, our approach represents a rare asymmetric H−heteroatom bond insertion by α-carbonyl sulfonium ylides, an attractive surrogate of diazocarbonyls. The mild intermolecular C–N bond formation was catalyzed by chiral phosphoric acids with excellent efficiency and enantiose-lectivity. The products are precursors to other important chiral amine derivatives, including drug molecules and chiral ligands. The enantioselectivity was controlled by dynamic kinetic resolution in the amination step, rather than the initial protonation. This process opens up a new platform for the development of other related insertion reactions.Funding Information
- Research Grants Council, University Grants Committee (16302318, 16302617)
- Ministry of Education of the People's Republic of China (12060093063, XK-1802-6)
- Natural Science Foundation of Beijing Municipality (2202040)
- National Natural Science Foundation of China (21402005, 91956114)
This publication has 49 references indexed in Scilit:
- Reversing Polarity: Carbonyl α‐Aminations with Nitrogen NucleophilesAngewandte Chemie, 2017
- Monoamine transporter and receptor interaction profiles of novel psychoactive substances: Para-halogenated amphetamines and pyrovalerone cathinonesEuropean Neuropsychopharmacology, 2015
- Catalytic Asymmetric Electrophilic Amination Reactions To Form Nitrogen-Bearing Tetrasubstituted Carbon StereocentersSynthesis, 2014
- Transition Metal Catalyzed Enantioselective α-Heterofunctionalization of Carbonyl CompoundsChemical Reviews, 2010
- Synthesis and Biological Evaluation of Bupropion Analogues as Potential Pharmacotherapies for Cocaine AddictionJournal of Medicinal Chemistry, 2009
- 1-(4-Methylphenyl)-2-pyrrolidin-1-yl-pentan-1-one (Pyrovalerone) Analogues: A Promising Class of Monoamine Uptake InhibitorsJournal of Medicinal Chemistry, 2006
- Asymmetric Construction of Quaternary Stereocenters by Direct Organocatalytic Amination of α-Substituted α-Cyanoacetates and β-Dicarbonyl CompoundsJournal of the American Chemical Society, 2004
- Enantioselective O- and N-Nitroso Aldol Synthesis of Tin Enolates. Isolation of Three BINAP−Silver Complexes and Their Role in Regio- and EnantioselectivityJournal of the American Chemical Society, 2004
- Catalytic Asymmetric Organozinc Additions to Carbonyl CompoundsChemical Reviews, 2001
- 1,2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric SynthesisChemical Reviews, 1996