Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*)

Sergio Rossi, Scott E. Denmark

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

The tremendous growth of interest in silicon chemistry was initially related to the ability of silicon to break the 'Lewis-Langmuir octet rule'. The chemistry of chiral, hypercoordinate silicon species has attracted increasing attention because of the capability of these compounds to catalyze a variety of stereoselective reactions. This chapter focuses on the interaction between the nonbonding electron pairs of the Lewis base (LB) donor and the o-antibonding orbitals of the silicon-based Lewis acid. When a silicon-based Lewis acid is involved in the formation of an acid-base adduct, a redistribution of the density over the peripheral ligands takes place. Such 'redistribution' results in bond lengthening as the coordination number of the Lewis acid increases with the expansion of the coordination sphere. The scope of Lewis base-catalyzed, Lewis acid-mediated reactions was expanded in 2003 to include stereoselective aldol additions of silyl enol ethers of achiral methyl ketones to aldehydes promoted by SiCl4 and catalyzed by phosphoramides.

Original languageEnglish (US)
Title of host publicationLewis Base Catalysis in Organic Synthesis
PublisherWiley-VCH Verlag
Pages1039-1076
Number of pages38
Volume3
ISBN (Electronic)9783527675142
ISBN (Print)9783527336180
DOIs
StatePublished - Aug 17 2016

Fingerprint

Lewis Bases
Lewis Acids
Silicon
Phosphoramides
Methyl Ethers
Ketones
Aldehydes
Ligands
Acids
Electrons

Keywords

  • Aldol reaction
  • Allylation reaction
  • Bisphosphoramide
  • Bisvinylogous aldol addition
  • Catalysis
  • Diastereoselectivity
  • Donor-acceptor interactions
  • Double aldol reaction
  • Electrophilic
  • Enantioselectivity
  • Glycolate aldol reaction
  • Hexacoordinate silicon
  • Hypercoordinate silicon
  • Hypervinylogous aldol reaction
  • Isocyanide
  • Lewis base
  • Passerini reaction
  • Pentacoordinate silicon
  • Phosphine oxides
  • Phosphoramides
  • Pinwheel conformation
  • Silicenium ions
  • Silyl enol ethers
  • Silyl ketene acetals
  • Silyl ketene imines
  • Silyl vinylketene imines
  • Stereoselective
  • Synthetic methods
  • Trichlorosilyl enol ethers
  • Trigonal bipyramidal silicon
  • Vinylogous aldol reaction
  • α-hydroxy amides
  • α-hydroxy esters

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Rossi, S., & Denmark, S. E. (2016). Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*). In Lewis Base Catalysis in Organic Synthesis (Vol. 3, pp. 1039-1076). Wiley-VCH Verlag. https://doi.org/10.1002/9783527675142.ch21

Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*). / Rossi, Sergio; Denmark, Scott E.

Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. p. 1039-1076.

Research output: Chapter in Book/Report/Conference proceedingChapter

Rossi, S & Denmark, SE 2016, Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*). in Lewis Base Catalysis in Organic Synthesis. vol. 3, Wiley-VCH Verlag, pp. 1039-1076. https://doi.org/10.1002/9783527675142.ch21
Rossi S, Denmark SE. Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*). In Lewis Base Catalysis in Organic Synthesis. Vol. 3. Wiley-VCH Verlag. 2016. p. 1039-1076 https://doi.org/10.1002/9783527675142.ch21
Rossi, Sergio ; Denmark, Scott E. / Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*). Lewis Base Catalysis in Organic Synthesis. Vol. 3 Wiley-VCH Verlag, 2016. pp. 1039-1076
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AB - The tremendous growth of interest in silicon chemistry was initially related to the ability of silicon to break the 'Lewis-Langmuir octet rule'. The chemistry of chiral, hypercoordinate silicon species has attracted increasing attention because of the capability of these compounds to catalyze a variety of stereoselective reactions. This chapter focuses on the interaction between the nonbonding electron pairs of the Lewis base (LB) donor and the o-antibonding orbitals of the silicon-based Lewis acid. When a silicon-based Lewis acid is involved in the formation of an acid-base adduct, a redistribution of the density over the peripheral ligands takes place. Such 'redistribution' results in bond lengthening as the coordination number of the Lewis acid increases with the expansion of the coordination sphere. The scope of Lewis base-catalyzed, Lewis acid-mediated reactions was expanded in 2003 to include stereoselective aldol additions of silyl enol ethers of achiral methyl ketones to aldehydes promoted by SiCl4 and catalyzed by phosphoramides.

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KW - Allylation reaction

KW - Bisphosphoramide

KW - Bisvinylogous aldol addition

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KW - Diastereoselectivity

KW - Donor-acceptor interactions

KW - Double aldol reaction

KW - Electrophilic

KW - Enantioselectivity

KW - Glycolate aldol reaction

KW - Hexacoordinate silicon

KW - Hypercoordinate silicon

KW - Hypervinylogous aldol reaction

KW - Isocyanide

KW - Lewis base

KW - Passerini reaction

KW - Pentacoordinate silicon

KW - Phosphine oxides

KW - Phosphoramides

KW - Pinwheel conformation

KW - Silicenium ions

KW - Silyl enol ethers

KW - Silyl ketene acetals

KW - Silyl ketene imines

KW - Silyl vinylketene imines

KW - Stereoselective

KW - Synthetic methods

KW - Trichlorosilyl enol ethers

KW - Trigonal bipyramidal silicon

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KW - α-hydroxy amides

KW - α-hydroxy esters

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