1240239-08-0Relevant articles and documents
Copper-catalyzed enantioselective propargylic amination of propargylic esters with amines: Copper-allenylidene complexes as key intermediates
Hattori, Gaku,Sakata, Ken,Matsuzawa, Hiroshi,Tanabe, Yoshiaki,Miyake, Yoshihiro,Nishibayashi, Yoshiaki
supporting information; experimental part, p. 10592 - 10608 (2010/09/10)
The scope and limitations of the copper-catalyzed propargylic amination of various propargylic esters with amines are presented, where optically active diphosphines such as Cl-MeO-BIPHEP and BINAP work as good chiral ligands. A variety of secondary amines are available as nucleophiles for this catalytic reaction to give the corresponding propargylic amines with a high enantioselectivity. The results of some stoichiometric and catalytic reactions indicate that the catalytic amination proceeds via copper-allenylidene complexes formed in situ, where the attack of amines to the electrophilic γ-carbon atom in the allenylidene complex is an important step for the stereoselection. Investigation of the relative rate constants for the reaction of several para-substituted propargylic acetates with N-methylanilines reveals that the formation of the copper-allenylidene complexes is involved in the rate-determining step. The result of the density functional theory calculation on a model reaction also supports the proposed reaction pathway involving copper-allenylidene complexes as key intermediates. The catalytic procedure presented here provides a versatile and direct method for the preparation of a variety of chiral propargylic amines.
