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Experimental determination of the absolute enantioselectivity of an anti body-catalyzed Diels-Alder reaction and theoretical explorations of the origins of stereoselectivity

Academic Article
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Overview

authors

  • Cannizzaro, C. E.
  • Ashley, J. A.
  • Janda, Kim
  • Houk, K. N.

publication date

  • March 2003

journal

  • Journal of the American Chemical Society  Journal

abstract

  • The exo and endo Diels-Alder adducts of p-methoxycarbonylbenzyl trans-1,3-butadiene-1-carbamate and N,N-dimethylacrylamide have been synthesized, and the absolute configurations of resolved enantiomers have been determined. On the basis of this information, the absolute enantioselectivities of the Diels-Alder reaction catalyzed by antibodies 13G5 and 4D5 as well as other catalytic antibodies elicited in the same immunizations have been established. The effects of different arrangements of catalytic residues on the structure and energetics of the possible Diels-Alder transition states were modeled quantum mechanically at the B3LYP/6-311++G**//B3LYP/6-31+G** level of theory. Flexible docking of these enantiomeric transition states in the antibody active site followed by molecular dynamics on the resulting complexes provided a prediction of the transition-state binding modes and an explanation of the origin of the observed enantioselectivity of antibody 13G5.

subject areas

  • Acrylamides
  • Amino Acid Sequence
  • Antibodies, Catalytic
  • Butadienes
  • Crystallography, X-Ray
  • Cyclization
  • Ferrous Compounds
  • Haptens
  • Kinetics
  • Models, Molecular
  • Molecular Conformation
  • Molecular Sequence Data
  • Molecular Structure
  • Quantum Theory
  • Stereoisomerism
  • Thermodynamics
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Identity

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja020879d

PubMed ID

  • 12603137
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Additional Document Info

start page

  • 2489

end page

  • 2506

volume

  • 125

issue

  • 9

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