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Rare‐Earth‐Metal‐Catalyzed Kinetic Resolution of Chiral Aminoalkenes via Hydroamination: The Effect of the Silyl Substituent of the Binaphtholate Ligand on Resolution Efficiency
- Source :
- European Journal of Organic Chemistry
- Publication Year :
- 2019
- Publisher :
- Wiley, 2019.
-
Abstract
- The kinetic resolution of α‐substituted aminopentenes via intramolecular hydroamination was investigated using various 3,3′‐silyl‐substituted binaphtholate yttrium catalysts. High efficiencies in the kinetic resolution were observed for methyl‐, benzyl‐, and phenyl‐substituted substrates utilizing the cyclohexyldiphenylsilyl‐substituted catalyst 2c with resolution factors reaching as high as 90(5) for hex‐5‐en‐2‐amine (3a). Kinetic analysis of the enantioenriched substrates with the matching and mismatching catalyst revealed that the efficiency of catalyst 2c benefits significantly from a favorable Curtin–Hammett pre‐equilibrium and by a large kfast/kslow ratio. Other binaphtholate catalysts were less efficient due to a less favorable Curtin–Hammett pre‐equilibrium, which often favored the mismatching substrate‐catalyst combination. Cyclization of the matched substrate proceeds generally with large trans‐selectivity, whereas the trans/cis‐ratio for mismatched substrates is significantly diminished, favoring the cis‐cyclization product isomer in some instances.
- Subjects :
- inorganic chemicals
Reaction mechanism
Reaction mechanisms
Substituent
010402 general chemistry
Photochemistry
01 natural sciences
Hydroamination
Catalysis
Kinetic resolution
chemistry.chemical_compound
Asymmetric catalysis
Rare earths
Physical and Theoretical Chemistry
Full Paper
010405 organic chemistry
Chemistry
Organic Chemistry
Enantioselective synthesis
Substrate (chemistry)
Full Papers
0104 chemical sciences
Intramolecular force
Asymmetric Hydroamination
Subjects
Details
- ISSN :
- 10990690 and 1434193X
- Volume :
- 2019
- Database :
- OpenAIRE
- Journal :
- European Journal of Organic Chemistry
- Accession number :
- edsair.doi.dedup.....4f1d3527f7754fb06bdcd8f7140aca29