Concise Total Synthesis of Lundurines A–C Enabled by Gold Catalysis and a Homodienyl Retro-Ene/Ene Isomerization

The total synthesis of lundurines A–C has been accomplished in racemic and enantiopure forms in 11–13 and 12–14 steps, respectively, without protection/deprotection of functional groups, by a novel tandem double condensation/Claisen rearrangement, a gold(I)-catalyzed alkyne hydroarylation, a cyclopropanation via formal [3 + 2] cycloaddition/nitrogen extrusion, and a remarkable olefin migration through a vinylcyclopropane retro-ene/ene reaction that streamlines the endgame.

• Publication year

  2016

• Venue

  Journal of the American Chemical Society

• Publication date

  2016-03-10

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/jacs.6b01428PMID 26963149PMCID 4819460
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Total synthesis of (-)-lundurine A and determination of its absolute configuration.

  2015cited by this paper
• Asymmetric total synthesis of (-)-lundurine B and determination of its absolute stereochemistry.

  2015cited by this paper
• Studies of a Diazo Cyclopropanation Strategy for the Total Synthesis of (-)-Lundurine A.

  2015cited by this paper
• An expeditious route to both enantiomers of all carbon quaternary stereocenters at C-3 carbon of lactams via [3,3]-sigmatropic rearrangement: total synthesis of (-)-physostigmine.

  2015cited by this paper
• The use of Mo Kα radiation in the assignment of the absolute configuration of light-atom molecules; the importance of high-resolution data.

  2014cited by this paper
• A concise and versatile synthesis of alkaloids from Kopsia tenuis: total synthesis of (±)-lundurine A and B.

  2014cited by this paper
• Total synthesis of (±)-lundurine B.

  2014cited by this paper
• Sequential 1,4- and 1,2-addition reactions to α,β-unsaturated N-acyliminium ions: a new strategy for the synthesis of spiro and bridged heterocycles.

  2013cited by this paper
• Iridium-catalyzed asymmetric hydrogenation of α-substituted α,β-unsaturated acyclic ketones: enantioselective total synthesis of (-)-mesembrine.

  2012cited by this paper
• Synthetic studies toward lapidilectine-type Kopsia alkaloids.

  2012cited by this paper
• Grandilodines A-C, biologically active indole alkaloids from Kopsia grandifolia.

  2011cited by this paper
• Direct Enantioselective Broensted Acid Catalyzed N‐Acyliminium Cyclization Cascades of Tryptamines and Ketoacids.

  2011cited by this paper
• Enantioselective synthesis of cyclic, quaternary oxonitriles.

  2010cited by this paper
• Efficient approach to androstene-fused arylpyrazolines as potent antiproliferative agents. Experimental and theoretical studies of substituent effects on BF(3)-catalyzed intramolecular [3 + 2] cycloadditions of olefinic phenylhydrazones.

  2009cited by this paper
• Synthesis of the tetracyclic core skeleton of the lundurines by a gold-catalyzed cyclization

  2009cited by this paper
• Enantioselective Brønsted acid-catalyzed N-acyliminium cyclization cascades.

  2009cited by this paper
• A Short Formal Synthesis of (±)-Perhydrohistrionicotoxin

  2008cited by this paper
• Synthesis of enantiopure 1-arylprop-2-en-1-ols and their tert-butyl carbonates.

  2008cited by this paper
• Intra- and intermolecular reactions of indoles with alkynes catalyzed by gold.

  2007cited by this paper
• Catalytic enantioselective allylation of ketoimines.

  2006cited by this paper
• Gold-catalyzed intramolecular reaction of indoles with alkynes: facile formation of eight-membered rings and an unexpected allenylation.

  2006cited by this paper
• Lundurines A-D, cytotoxic indole alkaloids incorporating a cyclopropyl moiety from Kopsia tenuis and revision of the structures of tenuisines A-C

  2004cited by this paper
• Precise absolute-structure determination in light-atom crystals

  2004cited by this paper
• Origins of boat or chair preferences in the Ireland-Claisen rearrangements of cyclohexenyl esters: a theoretical study.

  2003cited by this paper
• Lundurines A, B and C, new indole alkaloids with a novel carbon skeleton containing a cyclopropyl moiety

  1995cited by this paper
• Alkaloids of Kopsia lapidilecta

  1993cited by this paper
• A facile claisen rearrangement involving the transient tautomeric enamine forms of α-allyloxy and α-propargyloxyimines

  1992cited by this paper
• Remote control of stereogenicity transfer by ring-generated anisotropic orbital overlap. Stereochemistry of hydrogen shift in the intramolecular reverse ene reaction of a cis-2-alkyl-1-alkenylcyclopropane

  1991cited by this paper
• Stereochemistry of the thermal homodienyl hydrogen shift reverse ene reaction. Stereoelectronic control of stereogenicity transfer through the anisotropic influence of a cyclopropane ring

  1990cited by this paper
• Photochemistry of 1-carbomethoxy-6-methyltricyclo[4.3.1.04,6]Dec-2-en-10-one. preparation of a 1,3-cyclooctadiene

  1986cited by this paper
• Methods for indole alkaloid synthesis. A specific procedure for introducing the 6,7 double bond into Aspidosperma-type alkaloids via thiolactam dehydrogenation

  1986cited by this paper
• Synthesis of substituted 2-aminopent-4-enals and 2-amino-3-(2-furyl)propanals via[3,3]- and [1,3]-sigmatropic shifts of β-allyloxyenamines

  1984cited by this paper
• On enantiomorph‐polarity estimation

  1983cited by this paper
• Stereoselektive Cyclopropansynthesen durch ”︁Oxy‐Homodienylwasserstoffverschiebungen„

  1981cited by this paper
• Intramolecular cycloaddition reactions of olefinic tosylhydrazones

  1980cited by this paper
• SELECTIVITY IN RETRO-ENE VS. CYCLOPENTENE REARRANGEMENTS OF A CIS-METHYLVINYLCYCLOPROPANE

  1980cited by this paper
• Nutrition classics: Journal of American Chemical Society volume 60, 1939 pages 2719--2723 Pantothenic Acid. II. Its concentration and purification from liver.

  1979cited by this paper
• Dienyl and homodienyl 1,5-hydrogen shifts☆

  1966cited by this paper
• Reversible thermische Umlagerung von Bicyclo[5.1.0]octen‐(2) in Cyclooctadien‐(1.4)

  1965cited by this paper

• Dicobalt-catalyzed N=N coupling reactions of tertiary alkyl azides to form azoalkanes

  2025cites this paper
• Regio- and Enantioselective Pictet–Spengler Reaction of α-Diketones Catalyzed by a Single H-Bond Donor Organocatalyst

  2025cites this paper
• Total Syntheses of Grandilodines A and C and Lapidilectam via a Photoredox-Catalyzed Decarboxylative (6 + 2) Radical Annulation.

  2025cites this paper
• Asymmetric Synthesis of the Pentacyclic Framework of Kopsia Alkaloids

  2025cites this paper
• Gold(I)-Catalyzed Pathway-Switchable Syntheses of Azocine[4,5-b]indole and (1H-indol-3-yl)-Azepino[4,5-b]indole Derivatives.

  2025cites this paper
• Modular Approach in Synthesis of Polycyclic Indolizidine, Quinolizidine, and Related Alkaloids.

  2025cites this paper
• Divergent and Enantioselective Synthesis of Three Types of Chiral Polycyclic N‑Heterocycles via Copper-Catalyzed Dearomative Cyclization

  2025cites this paper
• Advances in the Synthesis of Cyclopropylamines.

  2025cites this paper
• Syntheses of Structurally Complex Marine Cyclopropyl-Diterpenoids: Peyssonnoside A and Its Aglycon.

  2025cites this paper
• Gold-catalyzed cyclization and cycloaddition in natural product synthesis.

  2024cites this paper
• Rhodium-Catalyzed Asymmetric Cyclopropanation of Indoles with N-Triftosylhydrazones.

  2024cites this paper
• Syntheses of Tetracyclic Indoline Derivatives Via Gold(I)-Catalyzed Hydroamination/Cycloisomerization Cascade of 2-Ethynyltryptamides.

  2024cites this paper
• Catalyst-Controlled Divergent Cycloisomerizations of N-Propargyl Indoles.

  2023cites this paper
• Recent asymmetric synthesis of natural products bearing an α-tertiary amine moiety via temporary chirality induction strategies.

  2023cites this paper
• Homogeneous Gold Catalysis for Regioselective Carbocyclization of Alkynyl Precursors.

  2023cites this paper
• Combining the best of both worlds: radical-based divergent total synthesis

  2023cites this paper
• Gold-catalyzed hydroarylation reactions: a comprehensive overview.

  2022cites this paper
• Total Synthesis of Natural Products using Gold Catalysis.

  2022cites this paper
• Total Synthesis of Spiro[cyclohexane-2-indoline] Alkaloids: A Regio- and Diastereoselective Spirocyclization Approach.

  2022cites this paper
• Ring contraction in synthesis of functionalized carbocycles.

  2022cites this paper
• Dinitrogen extrusion from diazene in organic synthesis

  2022cites this paper
• Catalytic Gold Chemistry: From Simple Salts to Complexes for Regioselective C-H Bond Functionalization.

  2021cites this paper
• Synthesis of octagon-containing molecular nanocarbons

  2021cites this paper
• Gold‐catalyzed intramolecular tandem cyclization of alkynol‐tethered alkylidenecyclopropanes to construct naphthalene‐fused eight‐ to eleven‐membered cyclic ethers

  2021cites this paper
• Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids.

  2021cites this paper
• Switching Chemoselectivity Based on the Ring Size: How to Make Ring-Fused Indoles Using Transition-Metal-Mediated Cross-Coupling

  2021cites this paper
• Access to Indole-Annulated Medium-Sized Lactams through Protonation/Deuteration-Induced Ring-Opening of Spiroindolines

  2021cites this paper
• Recent advances in applications of Heck reaction in the total synthesis of alkaloids

  2021cites this paper
• Applications of Diels–Alder cycloaddition reaction in total synthesis of alkaloids

  2021cites this paper
• Diastereoselective tricyclization/dimerization of yne-indoles catalyzed by a Au(III) complex featuring an L2/Z-type ligand

  2021cites this paper
• Concise Total Synthesis of Peyssonnoside A.

  2021cites this paper
• Asymmetric Catalytic Ketimine Mannich Reactions and Related Transformations

  2021cites this paper
• Strategic Use of Visible-Light Photoredox Catalysis in Natural Product Synthesis.

  2021cites this paper
• Lewis acid mediated cyclization: synthesis of 2 spirocyclohexylindolines.

  2021cites this paper
• Stereoselective Synthesis of Vinylcyclopropa[b]indolines via a Rh-Migration Strategy.

  2020cites this paper
• Gold-catalyzed cycloisomerization of enynamides: Regio- and stereoselective approach to tetracyclic spiroindolines

  2020cites this paper
• Buchwald‐Type Ligands on Gold(I) Catalysis

  2020cites this paper
• Catalytic Synthesis of 8‐Membered Ring Compounds via Cobalt(III)‐Carbene Radicals

  2020cites this paper
• Heteroarene-tethered Functionalized Alkyne Metamorphosis.

  2020cites this paper
• Tridentate Nickel(II)-Catalyzed Chemodivergent C-H Functionalization and Cyclopropanation: Regioselective and Diastereoselective Access to Substituted Aromatic Heterocycles.

  2020cites this paper
• Total synthesis of kopsinitarine E.

  2020cites this paper
• Synthesis of indoline-fused eight-membered azaheterocycles through Zn-catalyzed dearomatization of indoles and subsequent base-promoted C-C activation.

  2020cites this paper
• An Apparent Umpolung Reactivity of Indole via [Au]-Catalysed Cyclisation and Lewis-Acid Mediated Allylation.

  2020cites this paper
• Construction of Medium-Sized Rings by Gold Catalysis.

  2020cites this paper
• Gold-catalyzed homo- and cross-annulation of alkynyl carboxylic acids: a facile access to substituted 4-hydroxy 2H-pyrones and total synthesis of pseudopyronine A.

  2020cites this paper
• Sulfonyl Hydrazides in Organic Synthesis: A Review of Recent Studies

  2020cites this paper
• Eight-membered Rings With One Nitrogen

  2020cites this paper
• Total Synthesis of Kopsinitarine E

  2020cites this paper
• Enantioselective Formal Synthesis of (+)-Cycloclavine and Total Synthesis of (+)-5-epi-Cycloclavine.

  2019cites this paper
• Innovation in protecting-group-free natural product synthesis

  2019cites this paper
• Synthesis of Thioamides

  2019cites this paper
• Gold-catalyzed Iminations of Terminal Propargyl Alcohols with Anthranils with Atypical Chemoselectivity for C(1)-Additions and 1,2-Carbon Migration.

  2019cites this paper
• Gold(i)-catalyzed pathway-switchable tandem cycloisomerizations to indolizino[8,7-b]indole and indolo[2,3-a]quinolizine derivatives.

  2019cites this paper
• Divergent Strategy in Natural Product Total Synthesis.

  2018cites this paper
• Development of the Vinylogous Pictet-Spengler Cyclization and Total Synthesis of (±)-Lundurine A.

  2018cites this paper
• Collective Total Synthesis of (-)-Lundurines A-C.

  2018cites this paper
• Generation of Gold(I) Carbenes by Retro‐Buchner Reaction: From Cyclopropanes to Natural Products Synthesis

  2018cites this paper
• Co(III)/Zn(II)-catalyzed dearomatization of indoles and coupling with carbenes from ene-yne ketones via intramolecular cyclopropanation

  2018cites this paper
• Differentiating alkyne reactivity in the post-Ugi transformations: Access to polycyclic indole-fused frameworks

  2018cites this paper
• Gold‐Catalyzed Migration of Propargyl Acetate as an Entry into the Total Synthesis of Natural Products

  2018cites this paper
• Gold(I)‐Catalysis for the Synthesis of Terpenoids: From Intramolecular Cascades to Intermolecular Cycloadditions

  2018cites this paper
• Unified Total Synthesis of Pyrroloazocine Indole Alkaloids Sheds Light on Their Biosynthetic Relationship

  2018cites this paper
• Gold‐Catalyzed Hydrofunctionalizations and Spiroketalizations of Alkynes as Key Steps in Total Synthesis

  2018cites this paper
• Alkaloid Synthesis via Gold‐Catalyzed Carbon‐Carbon Bond Formation Using Enamine‐type Nucleophile

  2018cites this paper
• Gold‐Catalyzed Functionalization Reactions of Indole

  2018cites this paper
• Directing group assisted ZnI2-catalyzed cyclopropanation of indoles via 2-furylcarbenoids

  2018cites this paper
• Gold-Catalyzed Double Cycloisomerization of 1-Ene-4,10-diynyl Esters to Bicyclo[6.3.0]undeca-2,4,9-trienyl Esters.

  2018cites this paper
• Total syntheses of pyrroloazocine indole alkaloids: challenges and reaction discovery

  2018cites this paper
• Total Synthesis of Lapidilectine B Enabled by Manganese(III)-Mediated Oxidative Cyclization of Indoles.

  2018cites this paper
• Gold(I)-catalyzed access to neomerane skeletons

  2017cites this paper
• Synthesis of 2‐Substituted 2‐Amino Ketones by Rhodium‐Catalyzed Reaction of N‐Sulfonyl‐1,2,3‐triazoles with 2‐Alkenols

  2017cites this paper
• Gold‐Catalyzed Cyclizations of Alkynes with Alkenes and Arenes

  2017cites this paper
• A gold(i)-catalyzed intramolecular tandem cyclization reaction of alkylidenecyclopropane-containing alkynes.

  2017cites this paper
• Cyclopropanation Strategies in Recent Total Syntheses.

  2017cites this paper
• Broad scope gold(i)-catalysed polyenyne cyclisations for the formation of up to four carbon-carbon bonds.

  2017cites this paper
• Highly Enantioselective Copper- and Iron-Catalyzed Intramolecular Cyclopropanation of Indoles.

  2017cites this paper
• Hydroarylation of Alkynes using Cu, Ag, and Au Catalysts

  2017cites this paper
• Asymmetric amination of 2-substituted indolin-3-ones catalyzed by natural cinchona alkaloids

  2017cites this paper
• A catalyst-free 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines and 3-nitroindoles: an easy access to five-ring-fused tetrahydroisoquinolines

  2017cites this paper
• Total Synthesis of Lundurine and Related Alkaloids: Synthetic Approaches and Strategies.

  2017cites this paper
• Total Synthesis of (±)-Grandilodine B.

  2017cites this paper
• Automatic Reaction Pathway Search via Combined Molecular Dynamics and Coordinate Driving Method.

  2017cites this paper
• Gold(I)-Catalyzed Cycloisomerization of ortho-(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings.

  2017cites this paper
• Asymmetric Total Synthesis of Pentacyclic Indole Alkaloid Andranginine and Absolute Configuration of Natural Product Isolated from Kopsia arborea.

  2017cites this paper
• Synthesis of Spiro[piperidine‐3,3′‐oxindoles] via Gold(I)‐Catalyzed Dearomatization of N‐Propargyl‐ and N‐Homoallenyl‐2‐bromotryptamines

  2016cites this paper
• Total synthesis of (±)-ganocins B and C.

  2016cites this paper
• A Au(i)-catalyzed hydrogen bond-directed tandem strategy to synthesize indeno-chromen-4-one and indeno-quinolin-4-one derivatives.

  2016cites this paper
• Dual Photoredox/Gold Catalysis Arylative Cyclization of o-Alkynylphenols with Aryldiazonium Salts: A Flexible Synthesis of Benzofurans.

  2016cites this paper
• Ligand-controlled gold-catalyzed cycloisomerization of 1,n-enyne esters toward synthesis of dihydronaphthalene.

  2016cites this paper
• Synthesis of Chiral Aminocyclopropanes by Rare-Earth-Metal-Catalyzed Cyclopropene Hydroamination.

  2016cites this paper