Facile preparation of various heteroaromatic compounds via azatitanacyclopentadiene intermediates.

Coupling of acetylene, nitrile, and a titanium reagent, Ti(O-i-Pr)(4)/2 i-PrMgCl, generated new azatitanacyclopentadienes in a highly regioselective manner. Their subsequent reaction with sulfonylacetylene afforded pyridyltitanium compounds, which, upon reaction with electrophiles, gave substituted pyridines virtually as a single isomer. When optically active nitriles were used in this reaction, chiral pyridines were obtained without loss of the enantiopurity. Alternatively, the azatitanacyclopentadiene prepared from an unsymmetrical acetylene reacted with an aldehyde or another nitrile to give furans or pyrroles having four different substituents again in a regioselective manner.

• Publication year

  2005

• Venue

  Journal of the American Chemical Society

• Publication date

  2005-04-27

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/JA0502730PMID 15898797
• 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.

• Transition-metal-catalyzed reactions in heterocyclic synthesis.

  2004cited by this paper
• Construction of pyridine rings by metal-mediated [2 + 2 + 2] cycloaddition.

  2003cited by this paper
• Discovery of imidazole glycerol phosphate dehydratase inhibitors through 3-D database searching.

  2002cited by this paper
• Selective preparation of pyridines, pyridones, and iminopyridines from two different alkynes via azazirconacycles.

  2002cited by this paper
• Selective syntheses of metalated pyridines from two different unsymmetrical acetylenes, a nitrile, and a titanium(II) alkoxide.

  2002cited by this paper
• Ti(II)-mediated conversion of alpha-heterosubstituted (O, N, S) nitriles to functionalized cyclopropylamines. Effect of chelation on the cyclopropanation step.

  2002cited by this paper
• Metalative Reppe reaction. Organized assembly of acetylene molecules on titanium template leading to a new style of acetylene cyclotrimerization.

  2001cited by this paper
• Significant chemo- and regioselectivies in the Ru(II)-catalyzed [2+2+2] cycloaddition of 1,6-diynes with dicyanides.

  2001cited by this paper
• Cobalt-catalyzed alkyne-nitrile cyclotrimerization to form pyridines in aqueous solution.

  2000cited by this paper

• Recent advances in the transformation of nitriles into diverse N-heterocycles.

  2025cites this paper
• Photoredox-Catalyzed [2 + 1 + 2] Cyclization of Alkenes, Carbyne Equivalents, and Nitriles

  2025cites this paper
• Rapid and Controlled Assembly of Polysubstituted Furans and Their Oligoaryls from Alkynes and Aldehydes Facilitated by Sequential Deprotonation.

  2025cites this paper
• Schiff-base Polymer Immobilized Ruthenium for Efficient Catalytic Cross-coupling of Secondary Alcohols with γ-amino and 2-aminobenzyl Alcohols to Give Quinolines and Pyridines.

  2024cites this paper
• One-Pot Sequential Hydroamination Protocol for N-Heterocycle Synthesis: One Method To Access Five Different Classes of Tri-Substituted Pyridines.

  2023cites this paper
• Progress of Azametallacyclopentadienes in the New Century.

  2023cites this paper
• Direct synthesis of pentasubstituted pyrroles and hexasubstituted pyrrolines from propargyl sulfonylamides and allenamides

  2021cites this paper
• Tandem Synthesis of Tetrasubstituted NH Pyrroles from Simple Nitriles.

  2021cites this paper
• Robust Cobalt Catalyst for Nitrile/Alkyne [2+2+2] Cycloaddition: Synthesis of Polyarylpyridines and Their Mechanochemical Cyclodehydrogenation to Nitrogen-Containing Polyaromatics.

  2021cites this paper
• Synthesis of 2-Formylpyrroles from Pyridinium Iodide Salts.

  2020cites this paper
• Mechanistic Studies of Transition-Metal-Catalyzed [2 + 2 + 2] Cycloaddition Reactions.

  2020cites this paper
• Application of titanium catalysts for the syntheses of heterocycles

  2019cites this paper
• Formal [2+2+1] Synthesis of Tetrasubstituted Furans from Aldehydes, Acetylenedicarboxylates, and Acyl Compounds

  2019cites this paper
• Phosphine Ligand‐Free Ruthenium Complexes as Efficient Catalysts for the Synthesis of Quinolines and Pyridines by Acceptorless Dehydrogenative Coupling Reactions

  2019cites this paper
• Synthesis of Furans – Recent Advances

  2019cites this paper
• Six-Membered Heterocycles

  2019cites this paper
• [2+2+2] Cycloadditions of Alkynes with Heterocumulenes and Nitriles

  2019cites this paper
• CO 2 ‐Promoted C=N Bond Cleavage of Amidines Leading to Multi‐Substituted Pyridines

  2018cites this paper
• Copper-catalyzed [3 + 2 + 1] annulation for functionalized pyridines as potent and dynamic UV absorbers

  2018cites this paper
• Dual Roles of α,β-Unsaturated Oximes in Copper Catalyzed [3+3] Cyclization: Construction of 2,4,6-Trisubstituted Pyridines

  2018cites this paper
• MeOTf-Mediated Annulation of Alkylnitriles and Arylalkynes Leading to Polysubstituted NH-Pyrroles.

  2017cites this paper
• Oxidative Aza-Annulation of Enynyl Azides to 2-Keto/Formyl-1H-pyrroles.

  2017cites this paper
• Fe(II)/Au(I) Relay Catalyzed Propargylisoxazole to Pyridine Isomerization: Access to 6-Halonicotinates.

  2017cites this paper
• Regioselective Three-Component Reaction of Pyridine N-Oxides, Acyl Chlorides, and Cyclic Ethers.

  2017cites this paper
• A co-operative effect of visible light photo-catalysis and CoFe2O4 nanoparticles for green synthesis of furans in water

  2017cites this paper
• Oligomerization, Cyclooligomerization, Dimerization

  2017cites this paper
• Solvent-Free DABCO-Mediated [3 + 2] Cycloadditions of Donor-Acceptor Cyclopropanes with Aldehydes: Strategy for Synthesis of Fully Substituted Furans.

  2016cites this paper
• Manganese‐Catalyzed ortho‐C−H Alkenylation of Aromatic N−H Imidates with Alkynes: Versatile Access to Mono‐Alkenylated Aromatic Nitriles

  2016cites this paper
• Metal-Free Synthesis of Highly Substituted Pyridines by Formal [2+2+2] Cycloaddition under Mild Conditions.

  2016cites this paper
• Chapter 3 – Synthesized by Intermolecular Cyclizations

  2016cites this paper
• Synthesized by [2+2+1] Cyclization Reactions

  2016cites this paper
• Synthesized by Intramolecular Cyclizations

  2016cites this paper
• Zirconium-mediated multicomponent reactions of 1,3-butadiynes with ylidenemalononitriles to form functionalized 1,8-naphthyridine and cyclopenta[b]pyridine derivatives.

  2015cites this paper
• Modular synthesis of multisubstituted furans through palladium-catalyzed three-component condensation of alkynylbenziodoxoles, carboxylic acids, and imines.

  2015cites this paper
• Modular synthesis of tetra-substituted furans from alkynes, Weinreb amides, and aldehydes

  2015cites this paper
• Regioselective Pd-Catalyzed Synthesis of 2,3,6-Trisubstituted Pyridines from Isoxazolinones.

  2015cites this paper
• Unusual Nitrile–Nitrile and Nitrile–Alkyne Coupling of FcCN and FcCCCN

  2014cites this paper
• 5.34 Early Transition Metal Mediated Reductive Coupling Reactions

  2014cites this paper
• Palladium(II)-catalyzed cyclization of heterocyclic ketene aminals with (E)-ethyl 2,3-diiodoacrylates: selective synthesis of bicyclic pyrroles and bicyclic pyridones

  2014cites this paper
• Regioselective synthesis of enones via a titanium-promoted coupling of unsymmetrical alkynes with weinreb amides.

  2014cites this paper
• Ti(OiPr)4/nBuLi: an attractive reagent system for [2+2+2] cyclotrimerisation reactions.

  2014cites this paper
• Regiocontrolled gold-catalyzed [2+2+2] cycloadditions of ynamides with two discrete nitriles to construct 4-aminopyrimidine cores.

  2014cites this paper
• The efficient one-pot synthesis of tetraalkyl substituted furans from symmetrical acetylenes, EtAlCl2, and carboxylic esters catalyzed by Cp2TiCl2

  2014cites this paper
• Unusual nitrile-nitrile and nitrile-alkyne coupling of Fc-C≡N and FC-C≡C-C≡N.

  2014cites this paper
• Reactivity of a Seven‐Membered Zirconacyclocumulene towards CN Multiple Bonds – Formation of Metallaheterocycles by Insertion of C≡N and C=N Groups

  2014cites this paper
• Titanium-mediated cross-coupling reactions of 1,3-butadiynes with α-iminonitriles to 3-aminopyrroles: observation of an imino aza-Nazarov cyclization

  2014cites this paper
• Generation and Reactions of Heteroaromatic Lithium Compounds by Using In-Line Mixer in a Continuous Flow Microreactor System at Mild Conditions

  2013cites this paper
• Direct synthesis of pyridines and quinolines by coupling of γ-amino-alcohols with secondary alcohols liberating H2 catalyzed by ruthenium pincer complexes.

  2013cites this paper
• Synthesis of pyridines by carbenoid-mediated ring opening of 2H-azirines.

  2013cites this paper
• Reactions of Zirconocene Butadiyne or Monoyne Complexes with Nitriles: Straightfoward Synthesis of Functionalized Pyrimidines

  2013cites this paper
• Synthetic transformation of homopropargylic selenides to conjugated diene-substituted alcohols and amines using diisopropoxy(η2-alkyne)titanium intermediates

  2013cites this paper
• Transition metal-mediated synthesis of monocyclic aromatic heterocycles.

  2013cites this paper
• Rhodium-Catalyzed [2+2+2] Cycloaddition for the Synthesis of Substituted Pyridines, Pyridones, and Thiopyranimines

  2012cites this paper
• Transition metal-catalyzed carbocyclization of nitrogen and oxygen-tethered 1,n-enynes and diynes: synthesis of five or six-membered heterocyclic compounds.

  2012cites this paper
• Ruthenium-catalyzed [2+2+2] cycloaddition of diynes with nitriles in pure water.

  2012cites this paper
• Three-component coupling sequence for the regiospecific synthesis of substituted pyridines.

  2012cites this paper
• A simple and highly efficient iron catalyst for a [2+2+2] cycloaddition to form pyridines.

  2011cites this paper
• Cycloadditions and cyclizations of acetylenic, allenic, and conjugated dienyl sulfones.

  2010cites this paper
• Synthetic transformations mediated by the combination of titanium(IV) alkoxides and Grignard reagents: selectivity issues and recent applications. Part 2: Reactions of alkenes, allenes and alkynes

  2010cites this paper
• Approach to Trisubstituted 3-Aminopyrrole Derivatives by Yb(OTf)3-Catalyzed [4+1] Annulation of 2-Azadiene with Me3SiCN

  2010cites this paper
• Aliphatic aldehydes in the synthesis of carbo- and heterocycles. Part I. Synthesis of three-, four-, and five-membered rings

  2010cites this paper
• Multicomponent reactions for the synthesis of pyrroles.

  2010cites this paper
• Rhodium-catalyzed complete regioselective intermolecular cross-cyclotrimerization of aryl ethynyl ethers and nitriles or isocyanates at room temperature.

  2010cites this paper
• Recent strategies for the synthesis of pyridine derivatives.

  2010cites this paper
• Rh-catalyzed isomerization and intramolecular redox reaction of alkynyl ethers affording dihydropyrans and ketoolefins.

  2009cites this paper
• Über Reppe hinaus: Aufbau substituierter Arene durch [2+2+2]‐Cycloaddition von Alkinen

  2009cites this paper
• Beyond Reppe: building substituted arenes by [2+2+2] cycloadditions of alkynes.

  2009cites this paper
• A convenient titanium-mediated intermolecular alkyne–carbonate coupling reaction

  2009cites this paper
• Diene-titanium complexes as synthetic intermediates for the construction of three- or five-membered carbocycles.

  2008cites this paper
• Ethynyl p‐Tolyl Sulfone

  2007cites this paper
• Synthesis of Heterocyclic Systems by Transition‐Metal‐Catalyzed Cyclization‐Migration Reactions – A Diversity‐Oriented Strategy for the Construction of Spirocyclic 3(2H)‐Furanones and 3‐Pyrrolones

  2007cites this paper
• Practical preparation of N-(1-alkynyl)sulfonamides and their synthetic utility in titanium alkoxide-mediated coupling reactions

  2006cites this paper
• Synthesis of 2-amino-2,3-dihydrobenzofurans and fully substituted furans from modified Baylis–Hillman adducts

  2006cites this paper
• Ruthenium-catalyzed cycloaddition of 1,6-diynes and nitriles under mild conditions: role of the coordinating group of nitriles.

  2006cites this paper
• Cationic Rhodium(I)/Modified-BINAP Catalyzed [2+2+2] Cycloaddition of Alkynes with Nitriles

  2006cites this paper
• Regioselective construction of polysubstituted pyridine ring from Baylis–Hillman adducts via sequential introduction of tosylamide, Michael reaction, aldol condensation, and elimination of TsH

  2005cites this paper