A class II aldolase mimic.
[structures: see text] A class II aldolase-mimicking synthetic polymer was prepared by the molecular imprinting of a complex of cobalt (II) ion and either (1S,3S,4S)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4a) or (1R,3R,4R)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one (4b) in a 4-vinylpyridine-styrene-divinylbenzene copolymer. Evidence for the formation of interactions between the functional monomer and the template was obtained from NMR and VIS titration studies. The polymers imprinted with the template demonstrated enantioselective recognition of the corresponding template structure, and induced a 55-fold enhancement of the rate of reaction of camphor (1) with benzaldehyde (2), relative to the solution reactions, and were also compared to reactions with a series of reference polymers. Substrate chirality was observed to influence reaction rate, and the reaction could be competitively inhibited by dibenzoylmethane (6). Collectively, the results presented provide the first example of the use of enantioselective molecularly imprinted polymers for the catalysis of carbon-carbon bond formation.
Hedin-Dahlström
Jimmy
J
Bioorganic and Biophysical Chemistry Laboratory, Department of Chemistry and Biomedical Sciences,University of Kalmar, SE-391 82 Kalmar, Sweden.
Rosengren-Holmberg
Jenny P
JP
Legrand
Sacha
S
Wikman
Susanne
S
Nicholls
Ian A
IA
D000446:Aldehyde-Lyases / Q000037:antagonists & inhibitors / Q000737:chemistry* / Q000145:classification*; D001547:Benzaldehydes / Q000737:chemistry*; D002164:Camphor / Q000737:chemistry*; D002384:Catalysis; D047188:Chalcones / Q000737:chemistry / Q000494:pharmacology; D003035:Cobalt / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013997:Time Factors
D001547:Benzaldehydes; D047188:Chalcones; D007659:Ketones; D008024:Ligands; D009942:Organometallic Compounds; D011108:Polymers; D003035:Cobalt; D002164:Camphor; C061481:dibenzoylmethane; D000446:Aldehyde-Lyases; C032175:benzaldehyde