17. Rationalizing Reactivity and Selectivity in Aminocatalytic Reactions

  1. Peter I. Dalko
  1. Raghavan B. Sunoj

Published Online: 23 AUG 2013

DOI: 10.1002/9783527658862.ch17

Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications

Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications

How to Cite

Sunoj, R. B. (2013) Rationalizing Reactivity and Selectivity in Aminocatalytic Reactions, in Comprehensive Enantioselective Organocatalysis: Catalysts, Reactions, and Applications (ed P. I. Dalko), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527658862.ch17

Editor Information

  1. Université Paris-Descartes, PRES Sorbonne Paris Cité, CNRS, 45, rue des Saints-Pères, 75270 Paris Cedex 06, France

Publication History

  1. Published Online: 23 AUG 2013
  2. Published Print: 23 OCT 2013

ISBN Information

Print ISBN: 9783527332366

Online ISBN: 9783527658862

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Keywords:

  • density functional theory;
  • enamine;
  • iminium;
  • oxazolidinone;
  • transition states

Summary

This chapter provides an overview of energetic details on the formation of various intermediates that play vital roles in organocatalysis. The formation of intermediates such as enamine, iminium ion, and oxazolidinone under varying reaction conditions is described. While the discussions are primarily centered around the rich set of available computational studies, meaningful and balanced connections to pertinent insights obtained through experimental studies are also provided. The transition state models for rationalizing stereoselective bond formation between the nucleophile (generally an enamine) and a range of electrophiles are particularly emphasized. The factors contributing to stereoinduction in asymmetric organocatalytic reactions, such as steric shielding, weak stabilizing interactions hydrogen bonding, electrostatic and orbital interactions are described with the help of selected examples. The merits of general as well as refined transition state models for different reactions are compared and limitations delineated. The likely potential of the computational design of novel organocatalysts is discussed with a few interesting examples.