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Enantioselective Synthesis of α-(Hetero)aryl Piperidines Through Asymmetric Hydrogenation of Pyridinium Salts and Its Mechanistic Insights
- Publication Year :
- 2018
-
Abstract
- Enantioselective synthesis of α-aryl and α-heteroaryl piperidines is reported. The key step is an iridium-catalyzed asymmetric hydrogenation of substituted N-benzyl pyridinium salts. High levels of enantioselectivity up to 99.3:0.7 er were obtained for a range of α-heteroaryl piperidines. DFT calculations support an outer-sphere dissociative mechanism for the pyridinium reduction. Notably, initial protonation of the final enamine intermediate determines the stereochemical outcome of the transformation rather than hydride reduction of the resultant iminium intermediate.
- Subjects :
- Protonation
Pyridinium Compounds
010402 general chemistry
Iridium
01 natural sciences
Biochemistry
Medicinal chemistry
Article
Catalysis
Enamine
chemistry.chemical_compound
Piperidines
Physical and Theoretical Chemistry
Molecular Structure
010405 organic chemistry
Hydride
Aryl
Organic Chemistry
Asymmetric hydrogenation
Enantioselective synthesis
Iminium
Stereoisomerism
0104 chemical sciences
chemistry
Models, Chemical
Pyridinium
Hydrogenation
Oxidation-Reduction
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Accession number :
- edsair.doi.dedup.....ea58d5693fceeb4c744ba3de80f4c7e0