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Organocatalysis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Organocatalysis is the acceleration of a chemical transformation by a small organic molecule that is not a metal complex and is regenerated during the catalytic cycle [1][2]. In advanced synthetic organic chemistry the concept is bounded by the exclusive use of organic compounds—typically amines, phosphoric acids, N-heterocyclic carbenes, or phosphines—as the catalytic species, thereby excluding transition-metal catalysis and biocatalysis as the primary mode of activation [2][3]. Essential features are a defined activation mode (enamine, iminium, Brønsted-acid, nucleophilic, or carbene umpolung), turnover of the organic catalyst, and, in asymmetric organocatalysis, a chiral catalyst that differentiates prochiral faces of the substrate [2]. N-Heterocyclic carbenes operate by forming covalent Breslow-type intermediates that invert the polarity of carbonyl carbon atoms [1]. Phosphine organocatalysts add to electron-deficient π-systems to generate zwitterionic intermediates that mediate a range of annulations and substitutions [4]. Dual manifolds that merge a photoredox cycle with an organocatalytic cycle remain organocatalytic with respect to the bond-forming activation of the organic substrate [2]. The concept is distinguished from ligand-assisted metal catalysis, in which the organic molecule is not itself the catalytic center.

  • organocatalysis
  • enamine activation
  • N-heterocyclic carbene
  • asymmetric catalysis

Advanced Synthetic Organic Chemistry • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Dieter Enders; Oliver Niemeier; Alexander Henseler; Organocatalysis by N-Heterocyclic Carbenes. Chem. Rev. 2007, 107, 5606-5655, 10.1021/cr068372z.
  2. David W. C. MacMillan; The advent and development of organocatalysis. Nature 2008, 455, 304-308, 10.1038/nature07367.
  3. Peter I. Dalko; Lionel Moisan; In the Golden Age of Organocatalysis. Angew. Chem. Int. Ed. 2004, 43, 5138-5175, 10.1002/anie.200400650.
  4. Hongchao Guo; Yi Chiao Fan; Zhanhu Sun; Yang Wu; Ohyun Kwon; Phosphine Organocatalysis. Chem. Rev. 2018, 118, 10049-10293, 10.1021/acs.chemrev.8b00081.
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