Exploiting the Electrophilic Properties of Indole Intermediates: New Options in Designing Asymmetric Reactions
Angewandte Chemie International EditionPublished 8 December 2011
Charles C. J. Loh, Dieter Enders
Citations147
SJR quartileQ1
SJR score5.55
SNIP2.47
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
This untapped potential of the indole heterocycle is critically examined, restricting it mainly to enantioselective annulations of 1Hindoles and new frontier developments in this field.
Abstract
Think electrophilic: While the classical π-excessive indole is well-known for its electrophilic substitutions at position C3, recent advances in asymmetric catalysis resulted in a surge in utilizing the less discussed electrophilic properties of iminium-type intermediates (see picture) in complex annulations of indoles. Advances in AuI catalysis also allow an umpolung of the classical indole C3 reactivity.
Keywords
Chemistry
Chemical ReviewsGold-Catalyzed Organic Reactions
3,208 Citations2007A. Stephen K. Hashmi
Important vinylgold intermediates, the transmetalation from gold to other transition metals, the development of new ligands for gold catalysis, and significant contributions from computational chemistry are other crucial points for the field highlighted here.
NatureThe advent and development of organocatalysis
2,351 Citations2008David W. C. MacMillan
My opinion on why the field of organocatalysis has blossomed so dramatically over the past decade is presented.
Angewandte Chemie International EditionCatalytic Carbophilic Activation: Catalysis by Platinum and Gold π Acids
2,308 Citations2007Alois Fürstner, Paul Davies
The ability of platinum and gold catalysts to effect powerful atom-economic transformations has led to a marked increase in their utilization and the application of platinum- and gold-catalyzed transformations in natural product synthesis is discussed.
Chemical ReviewsGold-Catalyzed Cycloisomerizations of Enynes: A Mechanistic Perspective
2,048 Citations2008Eloísa Jiménez‐Núñez, Antonio M. Echavarren
The proposed involvement of cyclopropyl metal carbenes of type 4 in the electrophilic activation of enynes by transition metals was first substantiated in reactions catalyzed by Pd(II), in which the initially formed cycloprostyl palladiumCarbenes undergo [4 + 2] cycloaddition with the double bond of the conjugate enyne.
NatureRelativistic effects in homogeneous gold catalysis
1,814 Citations2007David J. Gorin, F. Dean Toste
This Review draws on experimental and computational data to present the current understanding of homogeneous gold catalysis, focusing on previously unexplored reactivity and its application to the development of new methodology.
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 Society ReviewsOrganocatalysis—after the gold rush
1,272 Citations2009Søren Bertelsen, Karl Anker Jørgensen
This tutorial review will firstly sketch the basic developments in organocatalysis, focussing especially on the use of secondary amines as catalysts for the functionalization of aldehydes and alpha,beta-unsaturated aldeHydes, with emphasis on the mechanisms of the transformations and outline recent trends within central areas of this research topic.
Angewandte Chemie International EditionAsymmetric Aminocatalysis—Gold Rush in Organic Chemistry
1,252 Citations2008Paolo Melchiorre, Mauro Marigo +2 more
This Review describes this "Asymmetric Aminocatalysis Gold Rush" and charts the milestones in its development.
Chemical Society ReviewsGold and platinum catalysis—a convenient tool for generating molecular complexity
1,164 Citations2009Alois Fürstner
This critical review intends to familiarize the reader with the essence of pi-acid catalysis, in particular with reactions or reaction cascades effected by gold and platinum complexes.
Angewandte Chemie International EditionHomogeneous Gold Catalysis Beyond Assumptions and Proposals—Characterized Intermediates
1,127 Citations2010A. Stephen K. Hashmi
Angewandte ChemieKatalytische carbophile Aktivierung: Platin‐ und Gold‐π‐Säuren als Katalysatoren
944 Citations2007Alois Fürstner, Paul Davies
Chemical Society ReviewsChiral Brønsted acid catalyzed Friedel–Crafts alkylation reactions
757 Citations2009Shu‐Li You, Quan Cai +1 more
In this tutorial review, recent progress in the development of chiral Brønsted acid-catalyzed asymmetric Friedel-Crafts reactions is presented.
Chemical ReviewsCatalytic Asymmetric Friedel−Crafts Alkylation Reactions—Copper Showed the Way
757 Citations2008Thomas B. Poulsen, Karl Anker Jørgensen
Alkylation with Activated Alkenes and Carbonyl Compounds in Copper Complexes and Other Metal Complexes: The Incubation Period 2904-2904 3.2.1.
Journal of the American Chemical SocietyPalladium-Catalyzed Enantioselective C-3 Allylation of 3-Substituted-1<i>H</i>-Indoles Using Trialkylboranes
532 Citations2006Barry M. Trost, Jean Quancard
Angewandte Chemie International EditionOrganocatalysis Lost: Modern Chemistry, Ancient Chemistry, and an Unseen Biosynthetic Apparatus
530 Citations2007Carlos F. Barbas
Since the year 2000 there has been explosive growth in an area of catalytic asymmetric synthesis now known as organocatalysis, catalysis mediated solely by small organic molecules, and this chemistry not only provides for fascinating and efficient syntheses of chiral molecules but may serve to explain the emergence of homochirality in the prebiotic world.
Chemical Society ReviewsOrganocatalytic strategies for the asymmetric functionalization of indoles
502 Citations2010Giuseppe Bartoli, Giorgio Bencivenni +1 more
This critical review documents the development of organocatalytic indole alkylation strategies, until the end of 2009 (127 references).
Angewandte ChemieHomogene Gold‐Katalyse jenseits von Vermutungen und Annahmen – charakterisierte Intermediate
490 Citations2010A. Stephen K. Hashmi
Proceedings of the National Academy of SciencesEnantioselective organocatalytic construction of pyrroloindolines by a cascade addition–cyclization strategy: Synthesis of (–)-flustramine B
464 Citations2004Joel F. Austin, Sung-Gon Kim +3 more
Angewandte ChemieDie asymmetrische Aminokatalyse – Goldrausch in der organischen Chemie
462 Citations2008Paolo Melchiorre, Mauro Marigo +2 more
Chemical Society ReviewsGold-catalyzed decorations of arenes and heteroarenes with C–C multiple bonds
438 Citations2010Marco Bandini
Although the peculiar aptitude of gold salts/complexes for interaction with aromatic compounds (auration process) has long been known, the direct catalytic gold decoration of arenes, has risen to prominence only recently and is described in this tutorial review.
Angewandte Chemie International EditionOrganocatalyzed Enantioselective Fluorocyclizations
388 Citations2011O. Lozano, George Blessley +7 more
More than twenty examples for this cascade fluorination-cyclization, which is catalyzed by cinchona alkaloids and employs N-fluorobenzenesulfonimide as the electrophilic fluorine source have been explored, and an unprecedented catalytic asymmetric difluorocyclization has also been identified.
Angewandte ChemieKatalytische Funktionalisierung von Indolen in einer neuen Dimension
367 Citations2009Marco Bandini, Astrid Eichholzer
Journal of the American Chemical SocietyNine-Step Enantioselective Total Synthesis of (+)-Minfiensine
365 Citations2009Spencer B. Jones, Bryon Simmons +1 more
An enantioselective total synthesis of the Strychnos alkaloid (+)-minfiensine has been accomplished and was completed in nine chemical steps and 21% overall yield.
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 EditionGold‐Catalyzed Transformation of 2‐Alkynyl Arylazides: Efficient Access to the Valuable Pseudoindoxyl and Indolyl Frameworks
291 Citations2011Alexander Wetzel, Fabien Gagosz
A series of functionalized 2-alkynyl arylazides has been converted into 3-substituted indoles or 2,2-disubstituting indolin-3-ones in the presence of a gold(I) complex to trap the intermediate a-imino gold carbene.
Journal of the American Chemical SocietyRhodium-Catalyzed [3 + 2] Annulation of Indoles
279 Citations2009Yajing Lian, Huw M. L. Davies
These studies demonstrate that rhodium-catalyzed reactions of donor/acceptor carbenoids proceeding by means of zwitterionic intermediates can be carried out with very high asymmetric induction.
Angewandte Chemie International EditionUmpolung Reactivity of Indole through Gold Catalysis
247 Citations2011Biao Lu, Yingdong Luo +4 more
These results indicate that intermediate C is strongly electrophilic and hence less selective compared with p-3 vs. m-3 (~5), lower than that in the case of nitration (>10), suggesting that C might be even more electrophobic than NO2+.
Angewandte ChemieDie verlorene Organokatalyse: moderne Chemie, klassische Chemie und ein unbemerkter Biosynthesemechanismus
227 Citations2007Carlos F. Barbas
Journal of the American Chemical SocietyEnantioselective Synthesis of Pyrroloindolines by a Formal [3 + 2] Cycloaddition Reaction
216 Citations2010Lindsay M. Repka, Jane Ni +1 more
P(R)-BINOL·SnCl(4) was found to catalyze a formal [3 + 2] cycloaddition reaction between C(3)-substituted indoles and 2-amidoacrylates to provide pyrroloindolines, expected to facilitate the total synthesis of pyrroleindoline alkaloids.
Angewandte Chemie International EditionEnantioselective Intramolecular Aza‐Michael Additions of Indoles Catalyzed by Chiral Phosphoric Acids
179 Citations2010Quan Cai, Chao Zheng +1 more
The asymmetric N-alkylation of indoles proceeds in the absence of electron-withdrawing groups under acidic conditions in order to form Na6(CO3)(SO4), Na2SO4, and Na2CO3 bonds.
Catalytic Asymmetric Friedel–Crafts Alkylations
177 Citations2009Marco Bandini, Achille Umani‐Ronchi
Angewandte Chemie International EditionEnantioselective Phase‐Transfer‐Catalyzed Intramolecular Aza‐Michael Reaction: Effective Route to Pyrazino‐Indole Compounds
173 Citations2008Marco Bandini, Astrid Eichholzer +2 more
Angewandte Chemie International EditionEnantioselective Michael/Mannich Polycyclization Cascade of Indolyl Enones Catalyzed by Quinine‐Derived Primary Amines
145 Citations2011Quan Cai, Chao Zheng +2 more
Both the tricyclic and tetracyclic core of 1 has drawn considerable attention because of its complexity and frequent appearance in natural products and pharmaceuticals and an enantioselective cascade synthesis towards these scaffolds is highly desirable but poses a challenge given.
Angewandte ChemieOrganocatalyzed Enantioselective Fluorocyclizations
145 Citations2011O. Lozano, George Blessley +7 more
Angewandte Chemie International EditionDirect Asymmetric Hydrosilylation of Indoles: Combined Lewis Base and Brønsted Acid Activation
141 Citations2011You‐Cai Xiao, Chao Wang +3 more
The National Basic Research Program of China (973 Program)[2010CB833300] is a national basic research program of China that aims to promote basic and applied science.
Chemistry - A European JournalMerging Organocatalysis and Gold Catalysis: Enantioselective Synthesis of Tetracyclic Indole Derivatives through a Sequential Double Friedel–Crafts Type Reaction
139 Citations2011Charles C. J. Loh, Jan Badorrek +2 more
An efficient and highly enantioselective one-pot, multicatalytic, C2/C3-annulation of indoles, giving rise to tetracyclic, seven-membered-ring-containing derivatives is reported.
Chemical CommunicationsStereoselective synthesis of tetracyclic indolines via gold-catalyzed cascade cyclization reactions
132 Citations2011Gianpiero Cera, Pasquale Crispino +2 more
Chemistry - A European JournalAsymmetric Organocatalytic N‐Alkylation of Indole‐2‐carbaldehydes with α,β‐Unsaturated Aldehydes: One‐Pot Synthesis of Chiral Pyrrolo[1,2‐<i>a</i>]indole‐2‐carbaldehydes
127 Citations2009Liang Hong, Wangsheng Sun +3 more
The exploration of novel, concise methodologies that allow the rapid establishment of these polycyclic indole skeletons in a single operation is highly desired.
Chemistry - A European JournalThe Enantioselective, Organocatalyzed Diels–Alder Reaction of 2‐Vinylindoles with α,β‐Unsaturated Aldehydes: An Efficient Route to Functionalized Tetrahydrocarbazoles
121 Citations2010Changwu Zheng, Yingpeng Lu +5 more
The results of this research are presented into an efficient catalyst system for the Diels–Alder reaction by using simple prolinols as the catalysts and the application of this method in the synthesis of the core structure of the akuammiline alkaloid vincorine.
Angewandte ChemieGold‐Catalyzed Transformation of 2‐Alkynyl Arylazides: Efficient Access to the Valuable Pseudoindoxyl and Indolyl Frameworks
101 Citations2011Alexander Wetzel, Fabien Gagosz
Journal of the American Chemical SocietyAsymmetric C2−C3 Cyclopentannulation of the Indole Ring
97 Citations2009José Barluenga, Eva Tudela +2 more
Angewandte ChemieUmpolung Reactivity of Indole through Gold Catalysis
91 Citations2011Biao Lu, Yingdong Luo +4 more
Advanced Synthesis & CatalysisOrganocatalytic Multiple Cascade Reactions: A New Strategy for the Construction of Enantioenriched Tetrahydrocarbazoles
71 Citations2011Yi‐Ju Cao, Hong‐Gang Cheng +5 more
Angewandte ChemieEnantioselective Michael/Mannich Polycyclization Cascade of Indolyl Enones Catalyzed by Quinine‐Derived Primary Amines
67 Citations2011Quan Cai, Chao Zheng +2 more
Angewandte ChemieEnantioselective Phase‐Transfer‐Catalyzed Intramolecular Aza‐Michael Reaction: Effective Route to Pyrazino‐Indole Compounds
63 Citations2008Marco Bandini, Astrid Eichholzer +2 more
Angewandte ChemieEnantioselective Intramolecular Aza‐Michael Additions of Indoles Catalyzed by Chiral Phosphoric Acids
52 Citations2010Quan Cai, Chao Zheng +1 more