Neutral Coordinate‐Organocatalysts in Organic Synthesis: Allylation of Acylhydrazones with Allyltrichlorosilanes
Advanced Synthesis & CatalysisPublished 1 August 2004
Shū Kobayashi, Masaharu Sugiura, Chikako Ogawa
Citations96
SJR quartileQ1
SJR score0.93
SNIP0.92
Generate an AI Snapshot to get a quick, structured summary of this paper.
Study Snapshot
ObjectiveStudy objective
MethodsResearch methodology
PopulationPopulation studied
Sample sizeSample sizes
OutcomesStudy outcomes here
ResultsStudy results comes here
LimitationsResearch study limitations comes here
A concise AI-generated summary of the paper will appear here once you click Generate AI Snapshot.
Abstract
Abstract N,N ‐Dimethylformamide (DMF), sulfoxides, and phosphine oxides, etc., which are neutral, uncharged molecules and coordinate to silicon atoms of organosilicon reagents to activate nucleophilic addition, are defined as neutral coordinate‐organocatalysts (NCOs). In the presence of NCOs , allylation reactions of acylhydrazones, useful imine surrogates, using allyltrichlorosilanes proceed smoothly to afford the synthetically useful racemic and non‐racemic homoallylic amine derivatives in high yields with high diastereoselectivities.
Keywords
Chemistry
Chemical ReviewsCatalytic Enantioselective Addition to Imines
1,564 Citations1999Shū Kobayashi, Haruro Ishitani
Shū Kobayashi was born in 1959 in Tokyo, Japan and studied chemistry at the University of Tokyo and received his Ph.D. in 1988 (Professor T. Mukaiyama), and received the first Springer Award in Organometallic Chemistry in 1997.
Chemical ReviewsSelective reactions using allylic metals
1,562 Citations1993Yoshinori Yamamoto, Naoki Asao
Chemical ReviewsCatalytic Enantioselective Addition of Allylic Organometallic Reagents to Aldehydes and Ketones
1,227 Citations2003Scott E. Denmark, Jiping Fu
Chemical ReviewsRecent Developments in the Synthesis and Utilization of Chiral Sulfoxides
1,160 Citations2003Inmaculada Fernández, Noureddine Khiar
Chemical ReviewsReactivity of penta- and hexacoordinate silicon compounds and their role as reaction intermediates
1,133 Citations1993Claude Chuit, Robert J. P. Corriu +2 more
Angewandte Chemie International EditionEnantioselective Organocatalysis
1,116 Citations2001Peter I. Dalko, Lionel Moisan
Chemical ReviewsAdditions of Organometallic Reagents to CN Bonds: Reactivity and Selectivity
911 Citations1998Robert J. Bloch
Chemical ReviewsPolymer-Supported Organic Catalysts
770 Citations2003Maurizio Benaglia, Alessandra Puglisi +1 more
Chemical ReviewsRecoverable Catalysts and Reagents Using Recyclable Polystyrene-Based Supports
652 Citations2002Catherine Anne McNamara, Mark J. Dixon +1 more
This paper presents a meta-analysis of C-C Bond Formation Using Recyclable Resin-Based Reagents and Catalysts using Immobilized Oxidants as a Carrier for Reagent Attachment to Polymer Supports, and some of the mechanisms behind this formation are described.
Tetrahedron AsymmetryAsymmetric synthesis of amines by nucleophilic 1,2-addition of organometallic reagents to the CN-double bond
567 Citations1997Dieter Enders, Ulrich Reinhold
Journal of the American Chemical SocietyEnantioselective hydrogenation of the C:N group: a catalytic asymmetric reductive amination procedure
318 Citations1992Mark J. Burk, John E. Feaster
Journal of the American Chemical Society(<i>S</i>)-3,3‘-Dimethyl-2,2‘-biquinoline <i>N,N</i>‘-Dioxide as an Efficient Catalyst for Enantioselective Addition of Allyltrichlorosilanes to Aldehydes
314 Citations1998Makoto Nakajima, Makoto Saitô +2 more
The Journal of Organic ChemistryFacile and Highly Stereoselective Synthesis of Homoallylic Alcohols Using Organosilicon Intermediates
298 Citations1994Shu̅ Kobayashi, Koichi Nishio
The Journal of Organic ChemistryAsymmetric Allylation of Aldehydes with Chiral Lewis Bases
239 Citations1994Scott E. Denmark, Diane M. Coe +2 more
Journal of the American Chemical SocietyThe Catalytic Asymmetric Mannich-Type Reactions in Aqueous Media
217 Citations2002Shū Kobayashi, Tomoaki Hamada +1 more
The catalytic, diastereo- and enantioselective Mannich-type reaction of a hydrazono ester with silyl enol ethers in aqueous media has been successfully achieved with ZnF(2), a chiral diamine ligand, and trifluoromethanesulfonic acid.
Journal of the American Chemical SocietyCatalytic, Enantioselective Addition of Substituted Allylic Trichlorosilanes Using a Rationally-Designed 2,2‘-Bispyrrolidine-Based Bisphosphoramide
213 Citations2001Scott E. Denmark, Jiping Fu
Angewandte Chemie International EditionQuinox, a Quinoline‐Type <i>N</i>‐Oxide, as Organocatalyst in the Asymmetric Allylation of Aromatic Aldehydes with Allyltrichlorosilanes: The Role of Arene–Arene Interactions
212 Citations2003Andrei V. Malkov, L. Dufkova +2 more
Journal of the American Chemical SocietyCatalytic Asymmetric Allylation of Imines via Chiral Bis-π-allylpalladium Complexes
196 Citations1998Hiroyuki Nakamura, Kaori Nakamura +1 more
Journal of the American Chemical SocietyChiral Sulfoxides as Neutral Coordinate-Organocatalysts in Asymmetric Allylation of <i>N</i>-Acylhydrazones Using Allyltrichlorosilanes
186 Citations2003Shū Kobayashi, Chikako Ogawa +2 more
Asymmetric crotylations using (Z)- and (E)-crotyltrichlorosilanes showed a high level of stereospecificity with high enantioselectivity, especially when optically active chiral sulfoxides were used.
Organic LettersChiral 2,2‘-Bipyridine-Type <i>N</i>-Monoxides as Organocatalysts in the Enantioselective Allylation of Aldehydes with Allyltrichlorosilane
180 Citations2002Andrei V. Malkov, Monica Orsini +5 more
The Sakurai-Hosomi-type allylation of aromatic and heteroaromatic aldehydes can be catalyzed by the new heterobidenate bipyridine monoxide PINDOX with high enantioselectivities and sterochemical outcome is mainly controlled by the axial chirality in PindOX.
Journal of the American Chemical SocietyVery high 1,2- and 1,3-asymmetric induction in the reactions of allylic boron compounds with chiral imines
174 Citations1986Yoshinori Yamamoto, Kazuhiro Maruyama +2 more
Organic LettersA Novel Axially Chiral 2,2‘-Bipyridine <i>N,N</i><i>‘</i>-Dioxide. Its Preparation and Use for Asymmetric Allylation of Aldehydes with Allyl(trichloro)silane as a Highly Efficient Catalyst
171 Citations2002Toyoshi Shimada, Asato Kina +2 more
One of the dioxides, (R)-3,3'-bis(hydroxymethyl)-6,6'-diphenyl-2,2'-bipyridine N,N'-dioxide, exhibited extremely high catalytic activity for the asymmetric allylation of aldehydes with allyl(trichloro)silane.
Journal of the American Chemical SocietyFluoride ion catalyzed aldol reaction between enol silyl ethers and carbonyl compounds
170 Citations1977Ryōji Noyori, Kaoru Yokoyama +4 more
Journal of the American Chemical SocietyErythro-selective aldol reaction via tris(dialkylamino)sulfonium enolates
159 Citations1981Ryōji Noyori, Ikuo Nishida +1 more
The Journal of Organic ChemistryFluoride ion catalyzed aldol reaction between enol silyl ethers and carbonyl compounds
152 Citations1983Eiichi Nakamura, Makoto Shimizu +4 more
TetrahedronCatalytic asymmetric reductive amination of ketones via highly enantioselective hydrogenation of the CN double bond
148 Citations1994Mark J. Burk, J. P. MARTINEZ +2 more
Tetrahedron LettersFacile and highly stereoselective allylation of aldehydes using allyltrichlorosilanes in DMF
133 Citations1993Shū Kobayashi, Koichi Nishio
The Journal of Organic ChemistryChiral π-Allylpalladium-Catalyzed Asymmetric Allylation of Imines: Replacement of Allylstannanes by Allylsilanes
131 Citations1999Kaori Nakamura, Hiroyuki Nakamura +1 more
TetrahedronAsymmetric allylation with chiral formamide catalysts
125 Citations1999Katsuhiko Iseki, Shin Mizuno +2 more
The Journal of Organic ChemistryNew Lewis-Basic <i>N</i>-Oxides as Chiral Organocatalysts in Asymmetric Allylation of Aldehydes
124 Citations2003Andrei V. Malkov, Mark Bell +6 more
Solvent effects on the conversion and the level of asymmetric induction have been elucidated, and MeCN has been identified as the optimal solvent for these catalysts.
Chemical Society ReviewsNew methodologies for the synthesis of compound libraries
120 Citations1999Shu̅ Kobayashi
Angewandte Chemie International EditionHighly Enantioselective Allylation of Imines with a Chiral Zirconium Catalyst
115 Citations2001Thomas Gastner, Haruro Ishitani +2 more
Journal of the American Chemical SocietyOn the Mechanism of Catalytic, Enantioselective Allylation of Aldehydes with Chlorosilanes and Chiral Lewis Bases
111 Citations2000Scott E. Denmark, Jiping Fu
Organic LettersAsymmetric Construction of Quaternary Centers by Enantioselective Allylation: Application to the Synthesis of the Serotonin Antagonist LY426965
109 Citations2002Scott E. Denmark, Jiping Fu
Catalytic enantioselective allylation with a chiral bisphosphoramide was applied to the synthesis of LY426965, a serotonin antagonist, providing the adduct containing a stereogenic quaternary center with excellent diastereoselectivity and enantiOSElectivity.
Journal of the American Chemical SocietyThe Hydrogen Chloride-Catalyzed Racemization of Sulfoxides
109 Citations1964Kurt Mislow, Todd Simmons +2 more
Tetrahedron LettersA chiral formamide: Design and application to catalytic asymmetric synthesis
108 Citations1998Katsuhiko Iseki, Shin Mizuno +2 more
Journal of the American Chemical SocietyAsymmetric Intramolecular [3 + 2] Cycloaddition Reactions of Acylhydrazones/Olefins Using a Chiral Zirconium Catalyst
107 Citations2002Shū Kobayashi, Haruka Shimizu +3 more
The Journal of Organic ChemistryCatalytic, Enantioselective Alkylations of <i>N</i>,<i>O</i>-Acetals
106 Citations1999Dana Ferraris, Travis Dudding +3 more
The Journal of Organic ChemistryHomoallylamines from aldimines and allylstannanes
105 Citations1985Gary E. Keck, Eric J. Enholm
Journal of the American Chemical SocietyUnderstanding the Correlation of Structure and Selectivity in the Chiral-Phosphoramide-Catalyzed Enantioselective Allylation Reactions: Solution and Solid-State Structural Studies of Bisphosphoramide·SnCl<sub>4</sub> Complexes
105 Citations2003Scott E. Denmark, Jiping Fu
Complexation of bisphosphoramides, linked by various length methylene tethers, with tin tetrachloride was studied by both solution NMR spectroscopy and single-crystal X-ray crystallography and provided detailed information on the stereochemical environment relevant to the enantioselectivity of asymmetric allylation reactions.
Chemical CommunicationsCatalytic enantioselective allylation with chiral Lewis bases
102 Citations2002Scott E. Denmark, Jiping Fu
The conceptual framework for the creation of this new process and the interplay of mechanistic investigations and synthetic studies that have conspired to produce a useful new reaction are outlined.
The Journal of Organic ChemistryDiastereofacial selectivity in the reaction of allylic organometallic compounds with imines. Stereoelectronic effect of imine group
101 Citations1985Yoshinori Yamamoto, Toshiaki Komatsu +1 more
Journal of the American Chemical SocietyChiral Ligand-Controlled Asymmetric Conjugate Addition of Lithium Amides to Enoates
97 Citations2003Hirohisa Doi, Takeo Sakai +3 more
The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities.
Journal of the American Chemical SocietyHighly Stereoselective Synthesis of Homoallylic Amines Based on Addition of Allyltrichlorosilanes to Benzoylhydrazones
95 Citations2001Ryoji Hirabayashi, Chikako Ogawa +2 more
It was found that the reactions tolerated well the steric hindrance of hydrazones and allyltrichlorosilanes, and alpha-heteroatom-substituted chiral benzoylhydrazones can be readily converted to homoallylic amines in high yields without epimerization.
Journal of the American Chemical SocietyNew Concept in the Allylation of Aldehydes: Regiospecific Allylation of Aldehydes by an Allyl-Transfer Reaction of Homoallylic Alcohols
95 Citations1998Junzo Nokami, Kenji Yoshizane +2 more
Tetrahedron AsymmetrySelective synthesis of optically active allenic and homopropargylic alcohols from propargyl chloride
92 Citations2002Makoto Nakajima, Makoto Saitô +1 more
Chemistry - A European JournalTransition Metal Fluoride Complexes in Asymmetric Catalysis
88 Citations1999Brian L. Pagenkopf, Erick M. Carreira
Journal of the American Chemical SocietyNew and Stereoselective Synthesis of 1,4-Disubstituted Buten-4-ols (Homoallylic Alcohol α-Adducts) from the Corresponding γ-Isomers (3,4-Disubstituted Buten-4-ols) via an Acid-Catalyzed Allyl-Transfer Reaction with Aldehydes
86 Citations2000Shin‐ichi Sumida, Masanori Ohga +2 more
Journal of the American Chemical SocietyHighly Stereoselective Synthesis of Homoallylic Amines Based on Addition of Allyltrichlorosilanes to Benzoylhydrazones under Neutral Conditions
79 Citations1999Shū Kobayashi, Ryoji Hirabayashi
Journal of the American Chemical SocietyHighly stereoselective allylation of aldehydes with pentacoordinate allylsilicates in hydroxylic media. Discrimination between linear and .alpha.-branched alkanals
75 Citations1990Mitsuo Kira, Kazuhiko Sato +1 more
The Journal of Organic ChemistryUse of Acylhydrazones as Stable Surrogates of Unstable Imines in Allylation, Mannich-Type, and Cyanide Addition Reactions
72 Citations1999Kei Manabe, H Oyamada +2 more
Journal of Molecular Catalysis A ChemicalNew pyridine-derived N-oxides as chiral organocatalysts in asymmetric allylation of aldehydes
71 Citations2003Andrei V. Malkov, Mark Bell +3 more
Tetrahedron LettersAsymmetric allylation of aldehydes with allyltrichlorosilane promoted by chiral sulfoxides
69 Citations2003António Massa, Andrei V. Malkov +2 more
Chemical CommunicationsChiral sulfoxides in the enantioselective allylation of aldehydes with allyltrichlorosilane
67 Citations2003Gareth J. Rowlands, William Kentish Barnes
The use of chiral sulfoxides as Lewis base catalysts in the allylation of aldehydes with allyltrichlorosilane is reported.
Organic reactionsThe <scp>P</scp> ummerer Reaction of Sulfinyl Compounds
65 Citations1991Ottorino De Lucchi, U. Miotti +1 more
Tetrahedron AsymmetryAsymmetric allenylation of aliphatic aldehydes catalyzed by a chiral formamide
62 Citations1998Katsuhiko Iseki, Yoshichika Kuroki +1 more
Tetrahedron LettersLewis acid-mediated [3+2] cycloaddition between hydrazones and olefins
57 Citations2003Shu̅ Kobayashi, Ryoji Hirabayashi +3 more
Tetrahedron LettersUreas: New efficient Lewis base catalysts for the allylation of aldehydes
57 Citations1999Isabelle Chataigner, Umberto Piarulli +1 more
SynlettRare Earth Triflate-Catalyzed Addition Reactions of Acylhydrazones with Silyl Enolates. A Facile Synthesis of Pyrazolone Derivatives
53 Citations1998H Oyamada, Shū Kobayashi
Angewandte Chemie International EditionEnantioselective [1,2] Wittig Rearrangement Using an External Chiral Ligand
51 Citations1999Katsuhiko Tomooka, Kyoko Yamamoto +1 more
Tetrahedron LettersAdditive effects on ligand activated allylation of aldehydes by allyltrichlorosilane
49 Citations1997Joanne D. Short, Sandrine Attenoux +1 more
The Journal of Organic ChemistryStereoselective Synthesis of Both <i>syn- </i>and <i>anti</i>-<i>N</i>-<i>tert</i>-Alkylamines Using Highly Stereospecific Crotylation of Ketone-Derived Acylhydrazones with Crotyltrichlorosilanes
47 Citations2002Chikako Ogawa, Masaharu Sugiura +1 more
This is the first example of highly stereospecific crotylation of ketimine analogues leading to both syn- and anti-N'-tert-alkyl-N-benzoylhydrazines, and different reactivities between (Z)- and (E)-crotylsilanes in terms of yields and selectivities were observed.
Chemistry LettersChiral Zirconium-Catalyzed Asymmetric Mannich-Type Reactions Using Acylhydrazones as Imine Equivalents
46 Citations1998Shū Kobayashi, Yoshiki Hasegawa +1 more
Chemistry LettersLithium Acetate-Catalyzed Aldol Reaction between Aldehyde and Trimethylsilyl Enolate
45 Citations2003Takashi Nakagawa, Hidehiko Fujisawa +1 more
Chemical CommunicationsPolymer-supported formamides as reusable organocatalysts for allylation of aldehydes with allyltrichlorosilane
43 Citations2002Chikako Ogawa, Masaharu Sugiura +1 more
New types of polymer-supported formamide have been synthesized from chloromethylated resins and formamides and it was found that the polymers worked well as organocatalysts in the allylation of aldehydes with allyltrichlorosilane to afford homoallylic alcohols in high yields.
Organic & Biomolecular ChemistryPhosphine oxides as efficient neutral coordinate-organocatalysts for stereoselective allylation of N-acylhydrazones
42 Citations2004Chikako Ogawa, Hideyuki Konishi +2 more
Phosphine oxides were found to be efficient neutral coordinate-organocatalysts (NCOs) for the allylation of N-acylhydrazones and a polymer-supported phosphine oxide was also developed as an effective immobilized NCO.
SynlettUse of Acylhydrazones as Electrophiles in Mannich-Type Reactions, <i>β</i>-Lactam, Pyrazolidinone, and Pyrazolone Synthesis
35 Citations1998Shū Kobayashi, Takayuki Furuta +2 more
Tetrahedron Letters5-(4′-chloromethylphenyl)pentylpolystyrene resin (CMPP resin). A new linker resin for solid-phase organic synthesis under Lewis acidic conditions
34 Citations1997Shū Kobayashi, Mitsuhiro Moriwaki
Liebigs Annalen der ChemieDiastereoselective Addition of Crotylboronates to Oximes
34 Citations1987Reinhard W. Hoffmann, Andreas Endesfelder
Tetrahedron LettersPolymer-supported acylhydrazones. Use in Sc(OTf)3-catalyzed Mannich-type reactions providing an efficient method for the preparation of diverse pyrazolone derivatives
33 Citations1999Shu̅ Kobayashi, Takayuki Furuta +3 more
Journal of the American Chemical SocietyNovel route to racemization of sulfoxides
32 Citations1972G. MODENA, U. QUINTILY +1 more
Chemistry LettersRegiospecific and Diastereoselective Crotylation of Aldimines with Crotyltrifluorosilanes Activated by Fluoride Ions
31 Citations1991Mitsuo Kira, Takakazu Hino +1 more
Aliphatic and aromatic aldimines are crotylated in a regiospecific and diastereo selective manner by the reaction with (E)- and (Z)-crotyltrifluorosilanes in the presence of cesium fluoride to give homoallylamines in high yields.
SynlettLewis Acid-Catalyzed Allylation Reactions of Acylhydrazones with Tetraallyltin in Aqueous Media
31 Citations2001Shū Kobayashi, Tomoaki Hamada +1 more
MoleculesMichael and Acetal Aldol-Type Reactions on Solid-Phase. Use of the Swollen- Resin Magic Angle Spinning (SR-MAS) NMR Technique for the Development of the Solid-Phase Organic Reactions
29 Citations1998Shū Kobayashi, Ryo Akiyama +2 more
Pure and Applied ChemistryNew methods for high-throughput synthesis
12 Citations2001Shū Kobayashi, Ryo Akiyama
Journal of Synthetic Organic Chemistry JapanChiral Coordinating Agent-based Enantiocontrol in Carbanion Reactions.
10 Citations2001Katsuhiko Tomooka
Journal of Synthetic Organic Chemistry JapanAsymmetric Reaction of Organolithium Reagents Under Control of Chiral Ligand.
7 Citations2000Kiyoshi Tomioka, Masayoshi Hasegawa
Journal of Synthetic Organic Chemistry JapanChiral Lewis Base-Catalyzed Reactions Involving Hypervalent Silicates.
6 Citations2000Makoto Nakajima
…
