Multicatalytic Asymmetric Synthesis of Complex Tetrahydrocarbazoles via a Diels–Alder/Benzoin Reaction Sequence
Organic LettersPublished 16 February 2012
Yankai Liu, Manuel Nappi, Eduardo C. Escudero‐Adán, Paolo Melchiorre
Citations156
SJR quartileQ1
SJR score1.24
SNIP1.03
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
A straightforward synthesis of structurally and stereochemically complex tetrahydrocarbazoles has been devised by designing a multicatalytic, one-pot Diels-Alder/benzoin reaction sequence to stereoselectively access trans-fused tetracyclic indole-based compounds having four stereogenic centers with very high fidelity.
Abstract
Expanding upon the recently developed aminocatalytic asymmetric indole-2,3-quinodimethane strategy, a straightforward synthesis of structurally and stereochemically complex tetrahydrocarbazoles has been devised. The chemistry's complexity-generating power was further harnessed by designing a multicatalytic, one-pot Diels-Alder/benzoin reaction sequence to stereoselectively access trans-fused tetracyclic indole-based compounds having four stereogenic centers with very high fidelity.
Keywords
Chemistry
Chemical ReviewsSynthesis and Functionalization of Indoles Through Palladium-catalyzed Reactions
1,768 Citations2005Sandro Cacchi, Giancarlo Fabrizi
P palladium-catalyzed synthesis can provide access to fine chemicals, agrochemical and pharmaceutical intermediates, and active ingredients in fewer steps and with less waste than classical.
Nature ChemistryOrganocatalytic cascade reactions as a new tool in total synthesis
1,557 Citations2010Christoph Grondal, Matthieu Jeanty +1 more
The first applications of asymmetric organocatalytic cascade reactions to the total synthesis of natural products are presented, paving the way for a new and powerful strategy that can help to address these issues.
Angewandte Chemie International EditionCatalytic Functionalization of Indoles in a New Dimension
1,421 Citations2009Marco Bandini, Astrid Eichholzer
This Review emphasizes the achievements in the selective catalytic functionalization of indoles (C-C bond-forming processes) over the last four years.
Chemical ReviewsIsolation and Synthesis of Biologically Active Carbazole Alkaloids
1,395 Citations2002Hans‐Joachim Knölker, Kethiri R. Reddy
Angewandte Chemie International EditionDiphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes
1,257 Citations2005Yujiro Hayashi, Hiroaki Gotoh +2 more
Angewandte Chemie International EditionN‐Heterocyclic Carbene Catalyzed Domino Reactions
980 Citations2011André Grossmann, Dieter Enders
A critical consideration of domino, cascade, and tandem catalysis in the case of N-heterocyclic carbenes catalysts is presented and recent publications in this area are highlighted.
Angewandte Chemie International EditionEnantioselective Organocatalyzed α Sulfenylation of Aldehydes
956 Citations2005Mauro Marigo, Tobias C. Wabnitz +2 more
NatureCollective synthesis of natural products by means of organocascade catalysis
731 Citations2011Spencer B. Jones, Bryon Simmons +2 more
It is shown that the application of two nature-inspired techniques, namely organocascade catalysis and collective natural product synthesis, can facilitate the preparation of useful quantities of a range of structurally diverse natural products from a common molecular scaffold.
Chemistry - An Asian JournalRecent Advances in Multicatalyst Promoted Asymmetric Tandem Reactions
458 Citations2010Jian Zhou
The current achievement of this promising field of multicatalyst promoted asymmetric tandem reactions is discussed, including the advantages and difficulties of this research, and the strategies applied to address these problems.
Journal of the American Chemical SocietyAsymmetric Catalysis of Diels–Alder Reactions with in Situ Generated Heterocyclic <i>ortho</i>-Quinodimethanes
396 Citations2011Yankai Liu, Manuel Nappi +3 more
This work documents the first asymmetric catalytic Diels-Alder reaction of in situ generated heterocyclic ortho-quinodimethanes (oQDMs), reactive diene species that have never before succumbed to a catalytic approach.
Journal of the American Chemical SocietyTrienamines in Asymmetric Organocatalysis: Diels−Alder and Tandem Reactions
390 Citations2011Zhi‐Jun Jia, Hao Jiang +7 more
It is demonstrated that the merger of optically active secondary amines and polyenals generates reactive trienamine intermediates, which readily participate in Diels-Alder reactions with different classes of dienophiles, hence, providing a facile entry to highly complex molecular frameworks with excellent stereocontrol.
Journal of the American Chemical SocietyHighly Efficient Hydrogen-Bonding Catalysis of the Diels–Alder Reaction of 3-Vinylindoles and Methyleneindolinones Provides Carbazolespirooxindole Skeletons
360 Citations2011Bin Tan, Gloria Hernández‐Torres +1 more
Simple precursors and mild conditions were used to construct carbazolespirooxindole derivatives with high enantiopurity and structural diversity under H-bonding catalysis, which will allow diversity-oriented syntheses of this intriguing class of compounds.
Angewandte Chemie International EditionCycle‐Specific Organocascade Catalysis: Application to Olefin Hydroamination, Hydro‐oxidation, and Amino‐oxidation, and to Natural Product Synthesis
276 Citations2009Bryon Simmons, Abbas M. Walji +1 more
The combined application of iminium (Im) and enamine (En) catalysts can effect a range of valuable asymmetric transformations including 1,2-hydroamination, -hydro-oxidation, and -amino-Oxidation of olefins.
Journal of the American Chemical SocietyAsymmetric Synthesis of Functionalized Cyclopentanones via a Multicatalytic Secondary Amine/<i>N</i>-Heterocyclic Carbene Catalyzed Cascade Sequence
246 Citations2009Stephen P. Lathrop, Tomislav Rovis
A one-pot, asymmetric multicatalytic formal [3+2] reaction between 1,3-dicarbonyls and alpha,beta-unsaturated aldehydes is described to afford densely functionalized cyclopentanones with high enantioselectivities.
Journal of the American Chemical SocietyAsymmetric Diels−Alder Reactions of 2-Pyrones with a Bifunctional Organic Catalyst
229 Citations2007Yi Wang, Hongming Li +4 more
It is demonstrated the possibility of using cinchona alkaloid-derived organic molecules as acid−base bifunctional catalysts as catalysts to control the endo/exo selectivity in a Diels−Alder reaction.
Angewandte Chemie International EditionOrganocatalytic Asymmetric Diels–Alder Reactions of 3‐Vinylindoles
225 Citations2008Claudio Gioia, Agnès Hauville +3 more
This work presents the development of an unprecedented catalytic asymmetric Diels–Alder reaction of 3-vinylindoles 1 with different representative dienophiles 2 (Scheme 1).
ChemCatChemMulticatalysis: Advancing Synthetic Efficiency and Inspiring Discovery
175 Citations2010Lisa M. Ambrosini, Tristan H. Lambert
Accounts of Chemical ResearchThe indole 2-3-quinodimethane strategy for the synthesis of indole alkaloids
160 Citations1984Philip Magnus, Timothy Gallagher +2 more
Journal of the American Chemical SocietyAsymmetric Total Synthesis of Vindoline
134 Citations2010Daisuke Kato, Yoshikazu Sasaki +1 more
This work defined the use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade and developed a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline.
Angewandte Chemie International EditionAchieving Molecular Complexity by Organocatalytic One‐Pot Strategies—A Fast Entry for Synthesis of Sphingoids, Amino Sugars, and Polyhydroxylated α‐Amino Acids
129 Citations2009Hao Jiang, Petteri Elsner +4 more
A new enantioand diastereoselective one-pot protocol to access 4,5-disubstituted isoxazoline-Noxides and the possibility of an in situ entrapment is evaluated, thereby, generating a new class of chiral 1,2-dielectrophiles to participate in multiple-bond-forming cascade sequences.
Angewandte Chemie<i>exo</i>‐Selective Asymmetric Diels–Alder Reaction of 2,4‐Dienals and Nitroalkenes by Trienamine Catalysis
119 Citations2011Zhi‐Jun Jia, Quan Zhou +3 more
Angewandte ChemieAchieving Molecular Complexity by Organocatalytic One‐Pot Strategies—A Fast Entry for Synthesis of Sphingoids, Amino Sugars, and Polyhydroxylated α‐Amino Acids
117 Citations2009Hao Jiang, Petteri Elsner +4 more
Organic LettersAn Enantioselective Approach to Highly Substituted Tetrahydrocarbazoles through Hydrogen Bonding-Catalyzed Cascade Reactions
115 Citations2010Xu‐Fan Wang, Jia‐Rong Chen +3 more
A hydrogen bonding-mediated double Michael addition-aromatization cascade of 2-propenylindoles and nitroolefins has been disclosed and allows an efficient synthesis of diverse and structurally complex tetrahydrocarbazoles in good to excellent enantioselectivity and diastereoselectivities.
Chemical ScienceEnamine/carbene cascade catalysis in the diastereo- and enantioselective synthesis of functionalized cyclopentanones
107 Citations2011Kerem Ozboya, Tomislav Rovis
An enantioselective synthesis of complex cyclopentanones using aliphatic aldehydes and activated enones using chiral secondary amine and a chiral triazolium catalyst is reported.
Chemistry - A European JournalAsymmetric Trienamine Catalysis for the Construction of Structurally Rigid Cyclic α,α‐Disubstituted Amino Acid Derivatives
83 Citations2011Hao Jiang, Björn Gschwend +3 more
In the presence of a secondary amine catalyst, 2,4-dienals undergo highly regio- and stereoselective Diels—Alder reactions with olefinic azlactones.
European Journal of Organic ChemistryDual Secondary Amine/N‐Heterocyclic Carbene Catalysis in the Asymmetric Michael/Cross‐Benzoin Cascade Reaction of β‐Oxo Sulfones with Enals
83 Citations2011Dieter Enders, André Grossmann +2 more
Organic LettersDynamic Kinetic Asymmetric Synthesis of Five Contiguous Stereogenic Centers by Sequential Organocatalytic Stetter and Michael−Aldol Reaction: Enantioselective Synthesis of Fully Substituted Cyclopentanols Bearing a Quaternary Stereocenter
62 Citations2011Bor‐Cherng Hong, Nitin S. Dange +3 more
A synthesis of fully substituted cyclopentanes bearing a quaternary carbon center and five contiguous stereogenic centers has been achieved by sequential organocatalyzed Stetter and Michael-Aldol reactions of heteroaromatic aldehydes, nitroalkenes, and α,β-unsaturated aldeHydes via the [1 + 2 + 2] annulation strategy with dynamic kinetic asymmetric transformation and excellent enantioselectivities.
Organic LettersOrganocatalytic Iminium Ion/Carbene Reaction Cascade for the Formation of Optically Active 2,4-Disubstituted Cyclopentenones
54 Citations2011Christian Jacobsen, Kim L. Jensen +2 more
An organocatalytic iminium ion/N-heterocyclic carbene (NHC) cascade reaction between β-keto phenyltetrazolesulfones and α,β-unsaturated aldehydes, providing direct access to optically active 2,4-disubstituted cyclopent-2-enones, has been developed.