Catalytic, asymmetric preparation of ketene dimers from acid chlorides.
[reaction: see text] The cinchona alkaloid-catalyzed dimerization of monosubstituted ketenes generated in situ from the reaction of acid chlorides and diisopropylethylamine yields ketene dimers in high yields and enantioselectivities. This reaction tolerates sterically demanding and functionally diverse substituents. Kinetic studies suggest that the rate-determining step for the reaction is the deprotonation of the acid chloride by the tertiary amine to form ketene and that the stereochemistry-forming step is addition of an ammonium enolate with ketene.
Calter
Michael A
MA
Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, USA. calter@chem.rochester.edu
Orr
Robert K
RK
Song
Wei
W
D000143:Acids / Q000737:chemistry*; D002384:Catalysis; D002712:Chlorides / Q000737:chemistry*; D019281:Dimerization; D005030:Ethylenes / Q000138:chemical synthesis* / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D013237:Stereoisomerism
D000143:Acids; D002712:Chlorides; D005030:Ethylenes; D007659:Ketones; C008223:ketene