The First Organocatalytic Enantioselective Inverse‐Electron‐Demand Hetero‐Diels–Alder Reaction
Angewandte ChemiePublished 4 April 2003
Karsten Juhl, Karl Anker Jørgensen
Citations94
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
Mit einem chiralen Amin als Katalysator reagieren Aldehyde mit Enonen diastereo- und enantioselektiv in Hetero-Diels-Alder-Reaktionen mit inversem Elektronenbedarf (siehe Schema; PCC=Pyridiniumchlorochromat). Die Reaktion gelingt mit zahlreichen Aldehyden und Enonen und wurde im Hinblick auf den Katalysator optimiert.
Keywords
ChemistryBiochemistry, Genetics and Molecular Biology
Journal of the American Chemical SocietyProline-Catalyzed Direct Asymmetric Aldol Reactions
2,833 Citations2000Benjamin List, Richard A. Lerner +1 more
The finding that the amino acid proline is an effective asymmetric catalyst for the direct aldol reaction between unmodified acetone and a variety of aldehydes is reported.
Journal of the American Chemical SocietyNew Strategies for Organic Catalysis: The First Highly Enantioselective Organocatalytic Diels−Alder Reaction
1,667 Citations2000Kateri A. Ahrendt, Christopher J. Borths +1 more
Journal of the American Chemical SocietyAmino Acid Catalyzed Direct Asymmetric Aldol Reactions: A Bioorganic Approach to Catalytic Asymmetric Carbon−Carbon Bond-Forming Reactions
1,161 Citations2001Kandasamy Sakthivel, Wolfgang Notz +2 more
Direct asymmetric catalytic aldol reactions have been successfully performed using aldehydes and unmodified ketones together with commercially available chiral cyclic secondary amines as catalysts and the observed stereochemistry of the products is in accordance with the proposed transition state.
Accounts of Chemical ResearchChiral Bis(oxazoline) Copper(II) Complexes: Versatile Catalysts for Enantioselective Cycloaddition, Aldol, Michael, and Carbonyl Ene Reactions
1,048 Citations2000Jeffrey S. Johnson, David A. Evans
X-ray crystallography of the chiral complexes reveals a propensity for the formation of distorted square planar or square pyramidal geometries in catalyzed processes that exhibit excellent temperature-selectivity profiles.
Journal of the American Chemical SocietyThe Direct Catalytic Asymmetric Three-Component Mannich Reaction
733 Citations2000Benjamin List
Journal of the American Chemical SocietyThe First Direct and Enantioselective Cross-Aldol Reaction of Aldehydes
702 Citations2002Alan B. Northrup, David W. C. MacMillan
The first enantioselective catalytic direct cross-aldol reaction that employs nonequivalent aldehydes has been accomplished using proline as the reaction catalyst, and allows facile enantiOSElective access to a broad range of beta-hydroxy aldeHydes which are valuable intermediates in polyketide syntheses.
Journal of the American Chemical SocietyThe Proline-Catalyzed Direct Asymmetric Three-Component Mannich Reaction: Scope, Optimization, and Application to the Highly Enantioselective Synthesis of 1,2-Amino Alcohols
656 Citations2002Benjamin List, Peter Pojarliev +2 more
Proline-catalyzed direct asymmetric three-component Mannich reactions of ketones, aldehydes, and amines are developed and application to the highly enantioselective synthesis of 1,2-amino alcohols is presented.
Journal of the American Chemical SocietyCatalytic Asymmetric Synthesis of <i>anti-</i>1,2-Diols
642 Citations2000Wolfgang Notz, Benjamin List
Angewandte Chemie International EditionCatalytic Asymmetric Hetero-Diels–Alder Reactions of Carbonyl Compounds and Imines
637 Citations2000Karl Anker Jørgensen
This review will focus on the most important developments, and discuss the synthetic and mechanistic aspects of enantioselective hetero-Diels-Alder reactions of carbonyl compounds catalyzed by chiral Lewis acids.
Journal of the American Chemical SocietyEnantioselective Organocatalytic Indole Alkylations. Design of a New and Highly Effective Chiral Amine for Iminium Catalysis
620 Citations2002Joel F. Austin, David W. C. MacMillan
A new strategy for asymmetric access to this important pharmacaphore has been accomplished that involves the amine catalyzed alkylation of indoles with alpha,beta-unsaturated aldehydes through the design of a new chiral amine catalyst that exhibits improved reactivity and selectivity for iminium catalysis.
Organic LettersEfficient Proline-Catalyzed Michael Additions of Unmodified Ketones to Nitro Olefins
587 Citations2001Benjamin List, Peter Pojarliev +1 more
This novel reaction provides gamma-nitro ketones in modest enantioselectivity yet excellent yields as well as proline-catalyzed Michael addition of unmodified ketones to nitro olefins.
Journal of the American Chemical SocietyNew Strategies in Organic Catalysis: The First Enantioselective Organocatalytic Friedel−Crafts Alkylation
573 Citations2001Nick A. Paras, David W. C. MacMillan
This work reveals that the LUMO-lowering activation of α,β-unsaturated aldehydes using the reversible formation of iminium ions with chiral imidazolidinones 1 is a valuable platform for the development of enantioselective organocatalytic Diels−Alder reactions.
Journal of the American Chemical SocietyAsymmetric Catalytic Mannich Reactions Catalyzed by Urea Derivatives: Enantioselective Synthesis of <i>β</i>-Aryl-<i>β</i>-Amino Acids
551 Citations2002Anna G. Wenzel, Eric N. Jacobsen
Highly enantioselective addition reactions between silyl ketene acetals and N-Boc aldimines are catalyzed by the thiourea-based catalyst 1c, with aryl and heteroaromatic derivatives generally affording nearly quantitative yields of beta-amino ester product in up to 98% enantiOSElectivity.
Journal of the American Chemical SocietyDirect Catalytic Asymmetric α-Amination of Aldehydes
511 Citations2002Benjamin List
The first direct catalytic asymmetric alpha-amination of aldehydes is described herein, which gives alpha-amino aldeHydes in excellent yields and enantioselectivities.
Journal of the American Chemical SocietyNew Strategies for Organic Catalysis: The First Enantioselective Organocatalytic 1,3-Dipolar Cycloaddition
507 Citations2000Wendy S. Jen, John J. M. Wiener +1 more
This work reveals that the LUMO-lowering activation of α,β-unsaturated aldehydes using the reversible formation of iminium ions with chiral imidazolidinones 1 is a valuable platform for the development of enantioselective organocatalytic Diels−Alder reactions.
Organic LettersCatalytic Direct Asymmetric Michael Reactions: Taming Naked Aldehyde Donors
481 Citations2001Juan M. Betancort, Carlos F. Barbas
Direct catalytic enantio- and diastereoselective Michael addition reactions of unmodified aldehydes to nitro olefins using (S)-2-(morpholinomethyl)pyrrolidine as a catalyst are described.
Angewandte Chemie International EditionDirect Organo-Catalytic Asymmetricα-Amination of Aldehydes—A Simple Approach to Optically Activeα-Amino Aldehydes,α-Amino Alcohols, andα-Amino Acids
474 Citations2002Anders Bøgevig, Karsten Juhl +3 more
Journal of the American Chemical SocietyKinetic and Stereochemical Evidence for the Involvement of Only One Proline Molecule in the Transition States of Proline-Catalyzed Intra- and Intermolecular Aldol Reactions
471 Citations2002Linh Hoang, Sogole Bahmanyar +2 more
These results provide the foundation of a unified enamine catalysis mechanism of proline-catalyzed inter- and intramolecular aldol reactions, and are supported by B3LYP/6-31G* calculations.
Journal of the American Chemical SocietyThe First General Enantioselective Catalytic Diels−Alder Reaction with Simple α,β-Unsaturated Ketones
451 Citations2002Alan B. Northrup, David W. C. MacMillan
The first general approach to enantioselective catalysis of the Diels-Alder reaction with simple ketone dienophiles has been accomplished with the use of iminium catalysis and a new chiral amine catalyst has been developed that allows a variety of monodentate cyclic and acyclic ketones to successfully participate in enantiOSElective [4 + 2] cycloadditions.
Journal of the American Chemical SocietyA Highly Enantioselective Amino Acid-Catalyzed Route to Functionalized α-Amino Acids
425 Citations2002Armando Córdova, Wolfgang Notz +3 more
It is shown that a variety of optically active amino acids can be synthesized with proline catalysis, where an L-amino acid begets other L-AMino acids, and the results may stimulate thoughts concerning prebiotic syntheses of optical active amino amino acids based on this route.
Journal of the American Chemical SocietyA Highly Enantioselective Route to Either Enantiomer of Both α- and β-Amino Acid Derivatives
361 Citations2002Armando Córdova, Shinichi Watanabe +3 more
This report describes the unprecedented use of unmodified aldehydes as donors in a catalytic asymmetric Mannich-type reaction that provides facile access to substituted beta-lactams.
Journal of the American Chemical SocietyDirect <scp>l</scp>-Proline-Catalyzed Asymmetric α-Amination of Ketones
350 Citations2002Nagaswamy Kumaragurubaran, Karsten Juhl +3 more
Organic LettersCatalytic Asymmetric Conjugate Addition of Nitroalkanes to Cycloalkenones
318 Citations2000Stephen Hanessian, Vinh Pham
Nitroalkanes add to cyclic and acyclic enones in an enantioselective manner in the presence of catalytic quantities of L-proline and trans-2,5-dimethylpiperazine as excess additive.
Organic LettersDiamine-Catalyzed Asymmetric Michael Additions of Aldehydes and Ketones to Nitrostyrene
315 Citations2002Alexandre Alexakis, Olivier Andrey
The direct Michael addition of aldehydes and ketones to nitrostyrene, catalyzed by N-i-Pr-2,2'-bipyrrolidine, is described, and the desired 1,4-adducts are obtained in excellent yield with enantioselectivities up to 85% ee and dr up to 95:5 of the syn product.
The Journal of Organic ChemistryOrganocatalytic Asymmetric Conjugate Addition of Nitroalkanes to α,β-Unsaturated Enones Using Novel Imidazoline Catalysts
284 Citations2002Nis Halland, Rita G. Hazell +1 more
SynlettProline-Catalyzed Enantioselective Michael Additions of Ketones to Nitrostyrene
283 Citations2002Dieter Enders, Atsushi Seki
The Journal of Organic ChemistryProline-Catalyzed One-Step Asymmetric Synthesis of 5-Hydroxy-(2<i>E</i>)-hexenal from Acetaldehyde
269 Citations2001Armando Córdova, Wolfgang Notz +1 more
For the first time, the L-proline-catalyzed direct asymmetric self-aldolization of acetaldehyde is described affording (+)-(5S)-hydroxy-(2E)-hexenal 2 with ee's ranging from 57 to 90%.
The Journal of Organic ChemistryAsymmetric Michael Addition of Malonate Anions to Prochiral Acceptors Catalyzed by <scp>l</scp>-Proline Rubidium Salt
259 Citations1996Masahiko Yamaguchi, Tai Shiraishi +1 more
Chemical CommunicationsDirect catalytic asymmetric aldol reactions of aldehydes
249 Citations2002Anders Bøgevig, Nagaswamy Kumaragurubaran +1 more
The development of a direct catalytic enantioselective aldol reaction of aldehydes with activated carbonyl compounds catalyzed by chiral amines is presented and the potential demonstrated by the synthesis of optically active beta-hydroxycarboxylic acid derivatives is demonstrated.
Angewandte Chemie International EditionHighly Enantioselective Organocatalytic Conjugate Addition of Malonates toAcyclic α,β‐Unsaturated Enones
244 Citations2003Nis Halland, Pompiliu S. Aburel +1 more
Angewandte Chemie International EditionThe Application of L-Proline as an Enzyme Mimic and Further New Asymmetric Syntheses Using Small Organic Molecules as Chiral Catalysts
244 Citations2001Harald Gröger, Jörg Wilken
Accounts of Chemical ResearchCatalytic Asymmetric Addition Reactions of Carbonyls. A Common Catalytic Approach
220 Citations1999Karl Anker Jørgensen, Mogens Johannsen +3 more
Journal of the American Chemical SocietyAsymmetric Azidation−Cycloaddition with Open-Chain Peptide-Based Catalysts. A Sequential Enantioselective Route to Triazoles
204 Citations2002David Guérin, Scott J. Miller
Unambiguous enhancement of enantioselectivity in the conjugate addition of azide to alpha,beta-unsaturated carboxylate derivatives has been achieved, enabling application to a sequential asymmetric azidation/cycloaddition for the synthesis of optically enriched triazoles and triazolines.
Angewandte Chemie International EditionHighly Enantioselective Inverse-Electron-Demand Hetero-DielsâAlder Reactions of α,β-Unsaturated Aldehydes This work was supported by the NIH (GM-59316), with additional support from the Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung (postdoctoral fellowship to K.G.), and the National Science Foundation (predoctoral fellowship to D.E.C.). We are grateful to Dr. R. Staples for carrying out the X-ray crystal structure analysis of 1.
202 Citations2002Karl Gademann, David E. Chavez +1 more
Angewandte ChemieKatalytische asymmetrische Hetero-Diels-Alder-Reaktionen von Carbonylverbindungen und Iminen
163 Citations2000Karl Anker Jørgensen
Angewandte ChemieHighly Enantioselective Organocatalytic Conjugate Addition of Malonates to Acyclic α,β‐Unsaturated Enones
99 Citations2003Nis Halland, Pompiliu S. Aburel +1 more
Journal of the American Chemical SocietySynthetic studies in the brefeldin series: asymmetric enamine-enal cycloaddition and intramolecular Nozaki reactions
96 Citations1988Stuart L. Schreiber, Harold V. Meyers
Tetrahedron AsymmetryCatalytic enantioselective 1,3-dipolar cycloaddition of nitrones to cyclopent-1-enecarbaldehyde
86 Citations2002Staffan Karlsson, Hans‐Erik Högberg
Organic LettersOne-Pot Asymmetric Synthesis of β-Cyanohydroxymethyl α-Amino Acid Derivatives: Formation of Three Contiguous Stereogenic Centers
79 Citations2002Shinichi Watanabe, Armando Córdova +2 more
Angewandte ChemieDie Anwendung vonL-Prolin als Enzymmimetikum und weitere neue asymmetrische Synthesen mit kleinen organischen Molekülen als chiralen Katalysatoren
69 Citations2001Harald Gröger, Jörg Wilken
Angewandte ChemieHighly Enantioselective Inverse-Electron-Demand Hetero-DielsâAlder Reactions of α,β-Unsaturated Aldehydes This work was supported by the NIH (GM-59316), with additional support from the Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung (postdoctoral fellowship to K.G.), and the National Science Foundation (predoctoral fellowship to D.E.C.). We are grateful to Dr. R. Staples for carrying out the X-ray crystal structure analysis of 1.
62 Citations2002Karl Gademann, David E. Chavez +1 more
Tetrahedron LettersDiels-alder reactions of 2-acetyl-2-cyclohexenone with enol ethers and emamines
43 Citations1980Barry B. Snider
Archiv der PharmazieOxabenzomorphane: Synthese von 4‐Phenyl‐tetrahydropyran‐2‐carbonsäuren
15 Citations1986F. EIDEN, Walter Winkler