Very mild, enantioselective synthesis of propargylamines catalyzed by copper(I)-bisimine complexes.
The stereoselective addition of aryl- and alkylacetylene derivatives to imines was studied. The reaction is catalyzed by copper complexes of enantiomerically pure bisimines, readily prepared in very high yields from the commercially available binaphthyl diamine. A very simple experimental procedure allowed to obtain at room temperature optically active propargylamines in high yields and enantioselectivity. Interestingly, bisimine/copper(I) complexes were able to promote the direct, enantioselective, catalytic addition to imines of alkylacetylenes. The effects of catalyst loading and other reaction parameters on the stereochemical outcome of the transformation were investigated. The extremely convenient methodology, the mild reaction conditions, and the possibility of a modular approach for developing new and more efficient bisimine-based chiral ligands make the present methodology very attractive.
Centro di Eccellenza CISI and Dipartimento di Chimica Organica e Industriale, Università degli Studi di Milano, via Golgi 19 -20133- Milano, Italy.
Federica
F
Colombo
Maurizio
M
Benaglia
Simonetta
S
Orlandi
Fabio
F
Usuelli
Giuseppe
G
Celentano
D000114:Acetylene / Q000031:analogs & derivatives / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry; D000588:Amines / Q000138:chemical synthesis*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D010293:Pargyline / Q000031:analogs & derivatives*; D013237:Stereoisomerism
D000480:Alkynes; D000588:Amines; D007097:Imines; D008024:Ligands; C044736:phenylacetylene; D003300:Copper; D010293:Pargyline; D000114:Acetylene