Fe(III) halides as effective catalysts in carbon-carbon bond formation: synthesis of 1,5-dihalo-1,4-dienes, alpha,beta-unsaturated ketones, and cyclic ethers.

Iron(III) halides have proven to be excellent catalysts in the coupling of acetylenes and aldehydes. When terminal acetylenes were used the main products obtained were 1,5-dihalo-1,4-dienes with (E,Z)-stereochemistry contaminated in some cases with (E)-alpha,beta-unsaturated ketones. The former carbonyl derivatives were the sole products isolated when nonterminal aromatic alkynes were used. When homopropargylic alcohols were used, a Prins-type cyclization occurred yielding 2-alkyl-4-halo-5,6-dihydro-2H-pyrans. In addition, anhydrous ferric halides are also shown to be excellent catalysts for the standard Prins cyclization with homoallylic alcohols. Isolation of an intermediate acetal, calculations, and alkyne hydration studies provide substantiation of a proposed mechanism.

• Publication year

  2005

• Venue

  Journal of Organic Chemistry

• Publication date

  Unknown publication date

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/jo048410j.s001PMID 15624906
• 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 (-)-apicularen A.

  2004cited by this paper
• Iron-catalyzed cross-coupling of primary and secondary alkyl halides with aryl grignard reagents.

  2004cited by this paper
• The "aqueous" Prins reaction.

  2003cited by this paper
• Iron(III) chloride-catalyzed convenient one-pot synthesis of homoallyl benzyl ethers starting from aldehydes.

  2003cited by this paper
• Stereoselective synthesis of cyclic ethers by intramolecular trapping of dicobalt hexacarbonyl-stabilized propargylic cations.

  2003cited by this paper
• Iron(III)-catalyzed Prins-type cyclization using homopropargylic alcohol: a method for the synthesis of 2-alkyl-4-halo-5,6-dihydro-2H-pyrans.

  2003cited by this paper
• A versatile indium trichloride mediated Prins-type reaction to unsaturated heterocycles.

  2003cited by this paper
• Marine natural products.

  2002cited by this paper
• Iron-catalyzed cross-coupling reactions.

  2002cited by this paper
• A novel titanium tetrahalide-mediated carbon-carbon bond-forming reaction: regioselective synthesis of substituted (E,Z)-1,5-dihalo-1,4-dienes.

  2002cited by this paper
• A new reaction of aryl aldehydes with aryl acetylenes in the presence of boron trihalides.

  2002cited by this paper
• Enantiocontrolled synthesis of trialkyl-substituted stereogenic carbons. A general route to cis-3,5-dialkyl gamma-lactones

  2000cited by this paper
• Catalytic C-H/olefin coupling

  1994cited by this paper

• Fe(III)-based Eutectic Mixtures as Multi-Task and Reusable Reaction Media for Efficient and Selective Conversion of Alkynes into Carbonyl Compounds.

  2023cites this paper
• Alkynyl Prins carbocyclization cascades for the synthesis of linear-fused heterocyclic ring systems

  2022cites this paper
• Synthetic β-hydroxy ketone derivative inhibits cholinesterases, rescues oxidative stress and ameliorates cognitive deficits in 5XFAD mice model of AD

  2020cites this paper
• Metal-free POCl3 promoted stereoselective hydrochlorination of ethynylated azaheterocycles.

  2019cites this paper
• Synthesis of Unsymmetrical Aza-Ullazines by Intramolecular Alkynyl-Carbonyl Metathesis.

  2018cites this paper
• Domino Synthesis of 2,3-Dialkylidenetetrahydrofurans via Tandem Prins Cyclization-Skeletal Reorganization.

  2018cites this paper
• Exploitation of Cyclopropane Carbaldehydes to Prins Cyclization: Quick Access to ( E)-Hexahydrooxonine and Octahydrocyclopenta[ b]pyran.

  2018cites this paper
• Barluenga's reagent with HBF4 as an efficient catalyst for alkyne-carbonyl metathesis of unactivated alkynes.

  2016cites this paper
• Selective ruthenium-catalyzed hydrochlorination of alkynes: one-step synthesis of vinylchlorides.

  2015cites this paper
• Stereoselective Synthesis of Trisubstituted Vinyl Bromides by Addition of Alkynes to Oxocarbenium Ions

  2015cites this paper
• Iron(III)-Catalyzed Cycloisomerizations of Acetal-Vinylidenecyclopropanes: An Efficient Synthetic Route to 1,2-Disubstituted Cyclobutenes.

  2015cites this paper
• Formal homologous aldol reactions: interrupting the Nazarov cyclization via carboalkoxylation of alkynes.

  2014cites this paper
• An operationally simple approach to (E)-α-halo vinyl sulfides and their applications for accessing stereodefined trisubstituted alkenes.

  2013cites this paper
• Regioselective hydration of alkynes by ironIII Lewis/Brønsted catalysis.

  2012cites this paper
• Synthesis of substituted phenanthrene by iron(III)-catalyzed intramolecular alkyne-carbonyl metathesis.

  2012cites this paper
• FeCl3·6H2O-catalyzed alkenylation of indoles with aldehydes.

  2012cites this paper
• Facile synthesis of azaspirocycles via iron trichloride-promoted cyclization/chlorination of cyclic 8-aryl-5-aza-5-tosyl-2-en-7-yn-1-ols.

  2012cites this paper
• Bismuth(III) salts as synthetic tools in organic transformations.

  2012cites this paper
• Cyclizations of alkynes: revisiting Baldwin's rules for ring closure.

  2011cites this paper
• (1-Alkynyl)dicarbonylcyclopentadienyliron complexes as electron-rich alkynes in organic synthesis: BF3-mediated [2+2] cycloaddition/ring-opening providing (2-alkenyl-1-imino)iron complexes.

  2011cites this paper
• Iron-catalyzed redox radical cyclizations of 1,6-dienes and enynes.

  2010cites this paper
• Boron and Titanium(IV) Halide Mediated Reactions

  2010cites this paper
• Iron-promoted synthesis of substituted 1-halo-1,4-pentadienes by reaction of 1,3-diarylpropenes with ethynylbenzenes via sp(3) C-H bond activation.

  2010cites this paper
• Iron(III)-catalyzed cyclization of alkynyl aldehyde acetals: experimental and computational studies.

  2010cites this paper
• Titanium(IV) halide mediated coupling of alkoxides and alkynes: an efficient and stereoselective route to trisubstituted (E)-alkenyl halides.

  2009cites this paper
• Iron trichloride-promoted cyclization of o-alkynylaryl isocyanates: synthesis of 3-(chloromethylene)oxindoles.

  2009cites this paper
• A new catalytic Prins cyclization leading to oxa- and azacycles.

  2009cites this paper
• Iron(III)-catalyzed and air-mediated tandem reaction of aldehydes, alkynes and amines: an efficient approach to substituted quinolines.

  2009cites this paper
• Iron-promoted cyclization/halogenation of alkynyl diethyl acetals.

  2009cites this paper
• Factors controlling the alkyne prins cyclization: the stability of dihydropyranyl cations.

  2008cites this paper
• 5- And 6-exocyclic products, cis-2,3,5-trisubstituted tetrahydrofurans, and cis-2,3,6-trisubstituted tetrahydropyrans via Prins-type cyclization.

  2008cites this paper
• Boron trihalide mediated alkyne-aldehyde coupling reactions: a mechanistic investigation.

  2008cites this paper
• Antiproliferative activity of 2-alkyl-4-halopiperidines and 2-alkyl-4-halo-1,2,5,6-tetrahydropyridines in solid tumor cell lines.

  2007cites this paper
• One-pot synthesis and SAR study of cis-2,6-dialkyl-4-chloro-tetrahydropyrans.

  2006cites this paper
• Prins‐Type Synthesis and SAR Study of Cytotoxic Alkyl Chloro Dihydropyrans

  2006cites this paper
• The profound effect of fluorine substitution on the reactivity and regioselectivity of nucleophilic substitution reactions of strained heterocycles. A study of aziridine and its derivatives.

  2006cites this paper
• β′‐Hydroxy‐α,β‐unsaturated ketones: A new pharmacophore for the design of anticancer drugs. Part 2.

  2006cites this paper
• Iron(III)-promoted aza-Prins-cyclization: direct synthesis of six-membered azacycles.

  2006cites this paper
• Catalytic asymmetric prins cyclizations: cation generation and trapping with (BINAP)Pt dications.

  2006cites this paper
• The silylalkyne-Prins cyclization: stereoselective synthesis of tetra- and pentasubstituted halodihydropyrans.

  2006cites this paper
• Beta'-hydroxy-alpha,beta-unsaturated ketones: a new pharmacophore for the design of anticancer drugs.

  2006cites this paper
• Substitution of benzylic hydroxyl groups with vinyl moieties using vinylboron dihalides.

  2005cites this paper