DNA-based asymmetric catalysis: sequence-dependent rate acceleration and enantioselectivity.
This study shows that the role of DNA in the DNA-based enantioselective Diels-Alder reaction of azachalcone with cyclopentadiene is not limited to that of a chiral scaffold. DNA in combination with the copper complex of 4,4'-dimethyl-2,2'-bipyridine (Cu-L1) gives rise to a rate acceleration of up to 2 orders of magnitude compared to Cu-L1 catalysis alone. Furthermore, both the enantioselectivity and the rate enhancement prove to be dependent on the DNA-sequence. These features are the main reasons for the efficient and enantioselective catalysis observed with salmon testes DNA/Cu-L1 in the Diels-Alder reaction. The fact that absolute levels of stereocontrol can be achieved with a simple and weak DNA-binding complex like Cu-L1 is a clear demonstration of the power of the supramolecular approach to hybrid catalysis.
Boersma
Arnold J
AJ
Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Klijn
Jaap E
JE
Feringa
Ben L
BL
Roelfes
Gerard
G
D015082:2,2'-Dipyridyl / Q000737:chemistry; D000818:Animals; D002384:Catalysis; D047188:Chalcones / Q000737:chemistry*; D002942:Circular Dichroism; D003300:Copper / Q000737:chemistry; D003517:Cyclopentanes / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D004277:DNA, Single-Stranded / Q000737:chemistry; D007700:Kinetics; D008297:Male; D009690:Nucleic Acid Conformation; D009841:Oligonucleotides / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry; D012474:Salmon; D013237:Stereoisomerism; D013379:Substrate Specificity
D047188:Chalcones; D003517:Cyclopentanes; D004277:DNA, Single-Stranded; D009841:Oligonucleotides; D009942:Organometallic Compounds; D015082:2,2'-Dipyridyl; D003300:Copper; D004247:DNA