Formal Cycloaddition of Disubstituted Ketenes with 2-Oxoaldehydes Catalyzed by Chiral N-Heterocyclic Carbenes
The Journal of Organic ChemistryPublished 25 September 2008
Lin He, Hui Lv, Yanrong Zhang, Song Ye
Citations149
SJR quartileQ2
SJR score0.74
SNIP0.86
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.
TL;DR
Chiral N-hetereocyclic carbenes were found to be efficient catalysts for the formal [2 + 2] cycloaddition reactions of alkyl(aryl)ketenes with 2-oxoaldehydes to afford beta-lactones with alpha-quaternary-beta-tertiary stereocenters in high yields with good diastereoselectivities and excellent enantioselectivity.
Abstract
Chiral N-hetereocyclic carbenes were found to be efficient catalysts for the formal [2 + 2] cycloaddition reactions of alkyl(aryl)ketenes with 2-oxoaldehydes to afford beta-lactones with alpha-quaternary-beta-tertiary stereocenters in high yields with good diastereoselectivities and excellent enantioselectivities (up to 99% ee). Both alkyl(aryl)ketenes and diarylketene worked well in this reaction.
Keywords
Chemistry
Chemical ReviewsOrganocatalysis by N-Heterocyclic Carbenes
3,014 Citations2007Dieter Enders, Oliver Niemeier +1 more
The inversion of the classical reactivity (Umpolung) opens up new synthetic pathways in biochemical processes as nucleophilic acylations and in nature, the coenzyme thiamine (vitamin B1), a natural thiazolium salt, utilizes a catalytic variant of this concept in biochemical process as nucleophile acylation.
Journal of the American Chemical SocietyOn the Mechanism of Thiamine Action. IV.<sup>1</sup> Evidence from Studies on Model Systems
1,662 Citations1958Ronald Breslow
Angewandte Chemie International EditionOrganocatalyzed Conjugate Umpolung of α,β‐Unsaturated Aldehydes for the Synthesis of γ‐Butyrolactones
722 Citations2004Christian Burstein, Frank Glorius
Journal of the American Chemical Society<i>N</i>-Heterocyclic Carbene-Catalyzed Generation of Homoenolates: γ-Butyrolactones by Direct Annulations of Enals and Aldehydes
701 Citations2004Stephanie S. Sohn, E.L. Rosen +1 more
This process demonstrates an unprecedented reaction mode for the generation of nucleophilic carbanions with a multifunctional organocatalyst under exceptionally mild and convenient reaction conditions.
Angewandte Chemie International Edition in EnglishCatalyzed Addition of Aldehydes to Activated Double Bonds—A New Synthetic Approach
611 Citations1976Hermann Stetter
Angewandte Chemie International EditionAn Efficient Nucleophilic Carbene Catalyst for the Asymmetric Benzoin Condensation
452 Citations2002Dieter Enders, Ulrike Kallfass
Quaternary Stereocenters
406 Citations2005
Angewandte Chemie International EditionExtending Mechanistic Routes in Heterazolium Catalysis–Promising Concepts for Versatile Synthetic Methods
394 Citations2005Kirsten Zeitler
Journal of the American Chemical SocietyNucleophilic Carbene and HOAt Relay Catalysis in an Amide Bond Coupling: An Orthogonal Peptide Bond Forming Reaction
368 Citations2007Harit U. Vora, Tomislav Rovis
A catalyzed internal redox process provides a route from α- reducible aldehydes and amines to α-reduced amides and proceeds in excellent yields using a variety of primary and secondary alkyl and aryl amines.
Organic LettersChiral N-Heterocyclic Carbene Catalyzed Staudinger Reaction of Ketenes with Imines: Highly Enantioselective Synthesis of <i>N</i>-Boc β-Lactams
348 Citations2007Yanrong Zhang, Lin He +3 more
N-heterocyclic carbenes were demonstrated to be efficient catalysts for the Staudinger reaction of ketenes with N-tosyl, N-benzyloxycarbonyl, or N-tert-butoxy Carbonyl imines, and two possible catalytic pathways, initiated by the addition of NHC to ketenes or imines were discussed.
Journal of the American Chemical Society<i>N</i>-Heterocyclic Carbene-Catalyzed Reaction of Chalcones and Enals via Homoenolate: an Efficient Synthesis of 1,3,4-Trisubstituted Cyclopentenes
345 Citations2006Vijay Nair, Sreekumar Vellalath +2 more
Nucleophilic heterocyclic carbene-catalyzed cyclopentannulation of enals and chalcones via homoenolate has been observed for the first time and leads to a very efficient synthesis of 3,4-trans-disubstituted-1-arylcyclopentenes instead of the expected cyclopENTanones.
Journal of the American Chemical SocietyAsymmetric synthesis of (S)- and (R)-malic acid from ketene and chloral
299 Citations1982Hans Wynberg, Emiel G. J. Staring
ChemInformN‐Heterocyclic Carbene‐Catalyzed Reaction of Chalcones and Enals via Homoenolate: An Efficient Synthesis of 1,3,4‐Trisubstituted Cyclopentenes.
287 Citations2006Vijay Nair, Sreekumar Vellalath +2 more
Journal of the American Chemical SocietyUmpolung of Michael Acceptors Catalyzed by <i>N</i>-Heterocyclic Carbenes
269 Citations2006Christian A. Fischer, Sean W. Smith +2 more
N-Heterocyclic carbenes can catalyze beta-alkylations of a range of alpha,beta-unsaturated esters, amides, and nitriles that bear pendant leaving groups to form a variety of ring sizes through an unanticipated addition-tautomerization sequence.
Organic & Biomolecular ChemistryN-Heterocyclic carbene catalysed β-lactam synthesis
243 Citations2008Nicolas Duguet, Craig D. Campbell +2 more
N-Heterocyclic carbenes promote the formal [2+2] cycloaddition of ketenes with N-tosyl imines to give the corresponding beta-lactams in good to excellent isolated yields; chiral NHCs give beta-Lactam in high e.e. after crystallisation.
Journal of the American Chemical SocietyEnantioselective, NHC-Catalyzed Bicyclo-β-Lactam Formation via Direct Annulations of Enals and Unsaturated <i>N</i>-Sulfonyl Ketimines
243 Citations2007Ming He, Jeffrey W. Bode
A wide range of α,β-unsaturated aldehydes, including 3-alkyl derivatives, undergo N-heterocyclic carbene (NHC)-catalyzed annulations with N-sulfonyl ketimines under mild conditions to provide bicyc...
Journal of the American Chemical SocietyCinchona Alkaloid-Lewis Acid Catalyst Systems for Enantioselective Ketene−Aldehyde Cycloadditions
229 Citations2004Cheng Zhu, Xiaoqiang Shen +1 more
Asymmetric cinchona alkaloid-catalyzed acid chloride-aldehyde cyclocondensation reactions afford enantioenriched 4-substituted and 3,4-disubstituting beta-lactones with near perfect absolute and relative stereocontrol.
Journal of the American Chemical SocietyCatalytic Asymmetric Staudinger Reactions to Form β-Lactams: An Unanticipated Dependence of Diastereoselectivity on the Choice of the Nitrogen Substituent
190 Citations2005Elaine C. Lee, Brian L. Hodous +3 more
This communication describes the first catalytic enantioselective Staudinger reactions that preferentially furnish trans beta-lactams (trans = relationship of Ph to R1).
Journal of the American Chemical SocietyDirect Amination of Homoenolates Catalyzed by <i>N</i>-Heterocyclic Carbenes
170 Citations2008Audrey Chan, Karl A. Scheidt
This formal [3+2] cycloaddition between alpha,beta-unsaturated aldehydes and acylaryldiazenes, catalyzed by an N-heterocyclic carbene, produces substituted pyrazolidinones in good yields.
TetrahedronMethods for the synthesis of optically active β-lactones (2-oxetanones)
163 Citations1999Hong Woon Yang, Daniel Romo
Journal of the American Chemical SocietyCatalytic Asymmetric Acyl Halide−Aldehyde Cyclocondensation Reactions of Substituted Ketenes
161 Citations2003Scott G. Nelson, Cheng Zhu +1 more
Catalytic asymmetric acyl halide-aldehyde cyclocondensation reactions of alkyl-substituted ketenes with structurally diverse aldehydes provide cis-disubstituting beta-lactones with high enantioselectivity.
Journal of the American Chemical SocietyCatalytic Asymmetric Acyl Halide−Aldehyde Cyclocondensations. A Strategy for Enantioselective Catalyzed Cross Aldol Reactions
153 Citations1999Scott G. Nelson, Timothy J. Peelen +1 more
Angewandte Chemie International EditionAsymmetric Synthesis of Highly Substituted β‐Lactones by Nucleophile‐Catalyzed [2+2] Cycloadditions of Disubstituted Ketenes with Aldehydes
147 Citations2004Jonathan E. Wilson, Gregory C. Fu
Journal of the American Chemical SocietyEnantioselective Addition of Alcohols to Ketenes Catalyzed by a Planar-Chiral Azaferrocene: Catalytic Asymmetric Synthesis of Arylpropionic Acids
135 Citations1999Brian L. Hodous, J. Craig Ruble +1 more
The Journal of Organic ChemistryN-Heterocyclic Carbene Catalyzed Aza-Morita−Baylis−Hillman Reaction of Cyclic Enones with <i>N</i>-Tosylarylimines
131 Citations2007Lin He, Tengyue Jian +1 more
Crossover experiments show NHC can add to N-tosylarylimines in a reversible manner, which allows the addition of NHC to cyclic enones and thus catalyzes the aza-Mortia-Baylis-Hillman reaction.
Heterocyclesβ-Lactones: Intermediates for Natural Product Total Synthesis and New Transformations
125 Citations2004Daniel Romo, Yingcai Wang +1 more
Tetrahedron AsymmetrySynthesis of enantiopure triazolium salts from pyroglutamic acid and their evaluation in the benzoin condensation
123 Citations2008Dieter Enders, Jianwei Han
The Journal of Organic ChemistryAsymmetric Synthesis of Bicyclic β-Lactones via the Intramolecular, Nucleophile-Catalyzed Aldol Lactonization: Improved Efficiency and Expanded Scope
117 Citations2005Seong Ho Oh, Guillermo S. Cortez +1 more
The intramolecular, nucleophile-catalyzed, aldol lactonization (NCAL) process merges catalytic, asymmetric carbocycle synthesis with beta-lactone synthesis with greatly improved conversion and efficiency and shorter reaction times with no diminution of enantioselectivity.
Journal of the American Chemical SocietyCatalytic Asymmetric Assembly of Stereodefined Propionate Units: An Enantioselective Total Synthesis of (−)-Pironetin
116 Citations2006Xiaoqiang Shen, Andrew S. Wasmuth +3 more
Double diastereoselection in alkaloid-catalyzed acyl halide-aldehyde cyclocondensation reactions provides a strategy for realizing syn- or anti-selective propionate aldol additions from a common reaction manifold.
Organic Letters<i>N</i>-Heterocyclic Carbene Catalyzed Ring Expansion of 4-Formyl-β-lactams: Synthesis of Succinimide Derivatives
107 Citations2007Gongqiang Li, Yi Li +2 more
N-heterocyclic carbene has been employed as an efficient catalyst for ring expansion of 4-formyl-beta-lactams, allowing the facile synthesis of succinimide derivatives.
Organic LettersFormation of Disubstituted β-Lactones Using Bifunctional Catalysis
103 Citations2005Michael A. Calter, Olexandr A. Tretyak +1 more
Organic LettersBicyclic- and Tricyclic-β-lactones via Organonucleophile-Promoted Bis-Cyclizations of Keto Acids: Enantioselective Synthesis of (+)-Dihydroplakevulin
100 Citations2006Huda Henry‐Riyad, Changsuk Lee +2 more
A highly diastereoselective, nucleophile-promoted bis-cyclization process, employing readily available and tractable keto acid substrates, is described, which provides concise access to bicyclic- and tricyclic-beta-lactones bearing tertiary carbinol centers and quaternary carbons.
Organic Letters<i>C</i><sub>2</sub>-Symmetric Cu(II) Complexes as Chiral Lewis Acids. Catalytic, Enantioselective Cycloadditions of Silyl Ketenes
95 Citations2001David A. Evans, Jacob M. Janey
It was found that (trimethylsilyl)ketene (1) may also undergo a highly selective hetero Diels-Alder reaction with beta,gamma-unsaturated alpha-keto esters.
Journal of the American Chemical SocietyLewis Acidity Expressed in Neutral Electron-Rich Aluminum(III) Complexes: An Example of Ligand-Defined Catalysis
75 Citations2000Scott G. Nelson, Beon-Kyu Kim +1 more
Organic LettersCatalytic Asymmetric Propionate Aldol Reactions via Acyl Halide−Aldehyde Cyclocondensations
66 Citations2000Scott G. Nelson, Zhonghui Wan
Lactone ring opening reveals that the enantiomerically enriched beta-lactones act as surrogates for syn propionate aldol adducts.
Organic LettersA Lewis Acid−Lewis Base Bifunctional Catalyst from a New Mixed Ligand
65 Citations2007Yun‐Ming Lin, Julie Boucau +5 more
The remarkable intramolecular bifunctional catalytic activity (1 mol % catalyst loading) of the new catalyst was demonstrated using a proof-of-principle reaction.
Angewandte Chemie International EditionCatalytic, Enantioselective Syntheses of β-Lactones—Versatile Synthetic Building Blocks in Organic Chemistry
59 Citations2002Christoph Schneider
Organic LettersEnantioselective β-Lactone Formation from Ketene and Aldehydes Catalyzed by a Chiral Oxazaborolidine
58 Citations2006Vijay Gnanadesikan, E. J. Corey
A novel catalytic system has been developed for the enantioselective synthesis of beta-lactones from ketene and aldehydes and its application in high-performance liquid chromatography is described.