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 language | English (US) |
|---|---|
| Title of host publication | Lewis Base Catalysis in Organic Synthesis |
| Publisher | Wiley-VCH Verlag |
| Pages | 1039-1076 |
| Number of pages | 38 |
| Volume | 3 |
| ISBN (Electronic) | 9783527675142 |
| ISBN (Print) | 9783527336180 |
| DOIs | |
| State | Published - Aug 17 2016 |
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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
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 proceeding › Chapter
}
TY - CHAP
T1 - Lewis Base-Catalyzed, Lewis Acid-Mediated Reactions (n → σ*)
AU - Rossi, Sergio
AU - Denmark, Scott E.
PY - 2016/8/17
Y1 - 2016/8/17
N2 - 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.
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.
KW - Aldol reaction
KW - Allylation reaction
KW - Bisphosphoramide
KW - Bisvinylogous aldol addition
KW - Catalysis
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
KW - Vinylogous aldol reaction
KW - α-hydroxy amides
KW - α-hydroxy esters
UR - http://www.scopus.com/inward/record.url?scp=85018247874&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85018247874&partnerID=8YFLogxK
U2 - 10.1002/9783527675142.ch21
DO - 10.1002/9783527675142.ch21
M3 - Chapter
AN - SCOPUS:85018247874
SN - 9783527336180
VL - 3
SP - 1039
EP - 1076
BT - Lewis Base Catalysis in Organic Synthesis
PB - Wiley-VCH Verlag
ER -