Asymmetric multicomponent copper catalyzed synthesis of chiral propargylamines

Journal of Molecular Catalysis A: Chemical

Volumn 260, Issue 1-2, 2006, Pages 128-134

  Colombo, Federica ^a   Benaglia, Maurizio ^a   Orlandi, Simonetta ^a   Usuelli, Fabio ^a  

^a UNIVERSITY OF MILAN   (Italy)

Author keywords

Asymmetric catalysis; Chiral copper(I) complexes; Chiral propargylamines; Multicomponent reactions; Phenylacetylene addition

Indexed keywords

ADDITION REACTIONS; ALDEHYDES; CATALYST SELECTIVITY; CATALYSTS; COPPER; SYNTHESIS (CHEMICAL);

ASYMMETRIC CATALYSIS; CHIRAL PROPARGYLAMINES; MULTICOMPONENT REACTIONS; PHENYLACETYLENE ADDITION;

AMINES;

EID: 33750533361     PISSN: 13811169     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.molcata.2006.07.003     Document Type: Article

References (36)

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30. In ancillaries experiments it was demonstrated that in these conditions copper(I)-bis-imine complexes were not able to promote the phenylacetylene addition to aldehydes.
31. Noteworthy the reaction did not afford any product in the presence of molecular sieves. A preliminary investigation by NMR tecniques have shown a marked decomposition of the copper(I)/bis-imine complex in the presence of molecular sieves. Further studies are currently underway in our group.
32. In a 95/5 toluene/water solution no product was obtained.
33. As expected, the (R)-binaphtyl amine/copper trifluoromethanesulfonate complex was not able to promote the multicomponent reaction, while it catalyzed the phenylacetylene addition to N-phenyl benzaldeyde imine in quantitative yield and 67% ee (see Ref. [15]).
34. The good level of enantioselectivity reached in the reaction is even more interesting considering that preliminary experiments have shown that it is possible to enrich the optical purity of the propargyl amines simply by recristallization. For example, for product 8, starting from a sample of 69% ee, one recristallization only afforded an enantiomerically pure compound (ee > 99%, by HPLC analysis; see: F. Colombo, M. Benaglia, S. Orlandi, F. Usuelli, G. Celentano, in preparation).
35. Also the reaction of 3,5-dinitrophenylacetylene with benzaldehyde and aniline was efficiently performed to give the corresponding chiral propargyl amine in 95% yield but 5% only enantiomeric excess. Further experiments on the topic are ongoing in our laboratories.
36. At the moment the results are quite puzzling; for example, it is not clear the role, if any, of the OH group of the chiral ligand and any attempt of rationalization would be highly speculative at this time.