Remote desymmetrization at near-nanometer group separation catalyzed by a miniaturized enzyme mimic.
The chirality of biological receptors often requires syntheses of therapeutic compounds in single enantiomer form. The field of asymmetric catalysis addresses enantioselective synthesis with chiral catalysts. Chemical differentiation of sites within molecules that are separated in space by long distances presents special challenges to chiral catalysts. As the distance between enantiotopic sites increases within a substrate, so too may the requirements for size and complexity for the catalyst. The extreme of catalyst complexity could be defined by macromolecular enzymes and their amazing capacity to effect stereospecific reactions over long distances between reactive sites and enzyme-substrate contacts. We report here a synthetic, miniaturized enzyme mimic that catalyzes a desymmetrization reaction over a very long distance.
Lewis
Chad A
CA
Department of Chemistry, Yale University, New Haven, CT 06520, USA.
Chiu
Anna
A
Kubryk
Michele
M
Balsells
Jaume
J
Pollard
David
D
Esser
Craig K
CK
Murry
Jerry
J
Reamer
Robert A
RA
Hansen
Karl B
KB
Miller
Scott J
SJ
D001713:Biphenyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D004798:Enzymes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D010455:Peptides / Q000737:chemistry; D012680:Sensitivity and Specificity; D013237:Stereoisomerism
D001713:Biphenyl Compounds; D004798:Enzymes; D010455:Peptides