Bifunctional and Synergistic Catalysis: Lewis Acid Catalysis and Lewis Base-Assisted Bond Polarization (n → σ*)

Won Jin Chung, Scott E. Denmark

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

One of the unique features of Lewis base catalysis is the capability of enhancing both nucleophilic and electrophilic characters within a molecule either through polarization or ionization of bonds upon coordination of a Lewis base onto the substrate. This chapter suggests to use either 'double activation catalysis' if both agents are acting on a single substrate or 'synergistic catalysis' if each agent activates a separate substrate. However, it is always possible that the Lewis base may simply serve as a ligand for the Lewis acid, which would constitute Lewis base activation of a Lewis acid. The chapter presents several leading accomplishments on the successful development of bifunctional or synergistic catalysis with mechanistic discussion as well as compilations of formally composed systems. The scope will be limited to the examples involving n Λ a*Lewis base activation, which is widely utilized for the addition of silylated nucleophiles to C=O or C=N double bonds.

Original languageEnglish (US)
Title of host publicationLewis Base Catalysis in Organic Synthesis
PublisherWiley-VCH Verlag
Pages1213-1258
Number of pages46
Volume3
ISBN (Electronic)9783527675142
ISBN (Print)9783527336180
DOIs
StatePublished - Aug 17 2016

Fingerprint

Lewis Bases
Lewis Acids
Catalysis
Polarization
Chemical activation
Substrates
Nucleophiles
Ionization
Ligands
Molecules

Keywords

  • Aldimines
  • Allyltrimethoxysilane
  • Aluminum-BINOL complex
  • Ammonium fluorides
  • Bifunctional catalysis (Lewis acid-Lewis base
  • Conjugate addition
  • Copper(I) enolate
  • Cyanohydrin
  • Diastereoconvergent
  • Double activation catalysis
  • Fluoride activation
  • Hosomi-Sakurai allylation
  • Ketimines
  • Lanthanide complexes
  • Lewis acid-Brønsted base)
  • Lewis base activation
  • Metallodienolate
  • Mukaiyama-Mannich reaction
  • Mukaiyama-aldol reaction
  • N -acylaziridines
  • N -acylpyrroles
  • N -acylquinolinium salts
  • N -heterocyclic carbene complex
  • N → σ
  • Nonlinear effect
  • Oxazaborolidinium salts
  • Phosphine oxide
  • Quinoline
  • Reissert reaction
  • Salen complexes
  • Silver(I) salts
  • Silylcyanation
  • Strecker reaction
  • Sulfonium fluorides
  • Synergistic catalysis
  • Trimethylsilyl cyanide
  • α; β-unsaturated δ-lactones

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Bifunctional and Synergistic Catalysis : Lewis Acid Catalysis and Lewis Base-Assisted Bond Polarization (n → σ*). / Chung, Won Jin; Denmark, Scott E.

Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. p. 1213-1258.

Research output: Chapter in Book/Report/Conference proceedingChapter

Chung, Won Jin ; Denmark, Scott E. / Bifunctional and Synergistic Catalysis : Lewis Acid Catalysis and Lewis Base-Assisted Bond Polarization (n → σ*). Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. pp. 1213-1258
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N2 - One of the unique features of Lewis base catalysis is the capability of enhancing both nucleophilic and electrophilic characters within a molecule either through polarization or ionization of bonds upon coordination of a Lewis base onto the substrate. This chapter suggests to use either 'double activation catalysis' if both agents are acting on a single substrate or 'synergistic catalysis' if each agent activates a separate substrate. However, it is always possible that the Lewis base may simply serve as a ligand for the Lewis acid, which would constitute Lewis base activation of a Lewis acid. The chapter presents several leading accomplishments on the successful development of bifunctional or synergistic catalysis with mechanistic discussion as well as compilations of formally composed systems. The scope will be limited to the examples involving n Λ a*Lewis base activation, which is widely utilized for the addition of silylated nucleophiles to C=O or C=N double bonds.

AB - One of the unique features of Lewis base catalysis is the capability of enhancing both nucleophilic and electrophilic characters within a molecule either through polarization or ionization of bonds upon coordination of a Lewis base onto the substrate. This chapter suggests to use either 'double activation catalysis' if both agents are acting on a single substrate or 'synergistic catalysis' if each agent activates a separate substrate. However, it is always possible that the Lewis base may simply serve as a ligand for the Lewis acid, which would constitute Lewis base activation of a Lewis acid. The chapter presents several leading accomplishments on the successful development of bifunctional or synergistic catalysis with mechanistic discussion as well as compilations of formally composed systems. The scope will be limited to the examples involving n Λ a*Lewis base activation, which is widely utilized for the addition of silylated nucleophiles to C=O or C=N double bonds.

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KW - Allyltrimethoxysilane

KW - Aluminum-BINOL complex

KW - Ammonium fluorides

KW - Bifunctional catalysis (Lewis acid-Lewis base

KW - Conjugate addition

KW - Copper(I) enolate

KW - Cyanohydrin

KW - Diastereoconvergent

KW - Double activation catalysis

KW - Fluoride activation

KW - Hosomi-Sakurai allylation

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KW - Lanthanide complexes

KW - Lewis acid-Brønsted base)

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KW - N -acylquinolinium salts

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KW - N → σ

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KW - Oxazaborolidinium salts

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KW - Quinoline

KW - Reissert reaction

KW - Salen complexes

KW - Silver(I) salts

KW - Silylcyanation

KW - Strecker reaction

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