Cooperative dual catalysis: application to the highly enantioselective conjugate cyanation of unsaturated imides.
Cooperative heterobimetallic catalysis was used as a design principle to achieve a highly reactive system for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides. A dual-catalyst pathway involving chiral (salen)Al complex 1b and chiral (pybox)Er complex 4b provides measurable improvements in rates and enantioselectivities relative to single-catalyst systems. Mechanistic studies point to a cooperative bimetallic mechanism involving activation of the imide by the Al complex and activation of cyanide by the Er complex.
Sammis
Glenn M
GM
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
Danjo
Hiroshi
H
Jacobsen
Eric N
EN
D000077410:Aluminum Chloride; D017607:Aluminum Compounds / Q000737:chemistry; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry; D005029:Ethylenediamines / Q000737:chemistry; D006856:Hydrogen Cyanide / Q000737:chemistry*; D007094:Imides / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D017607:Aluminum Compounds; D002712:Chlorides; D005029:Ethylenediamines; D007094:Imides; D028581:Lanthanoid Series Elements; D009942:Organometallic Compounds; D006856:Hydrogen Cyanide; D000077410:Aluminum Chloride; C011452:disalicylaldehyde ethylenediamine