Cobalt-Catalyzed Stereoselective Synthesis of 2,5- trans-THF Nitrile Derivatives as a Platform for Diversification: Development and Mechanistic Studies.

A straightforward protocol integrating a sustainable approach for the synthesis of new 2,5- trans-THF nitrile derivatives enabling an easy diversification of its side chain scaffolds is described. The reaction tolerated different aromatic and alkyl substituents, affording the corresponding 2,5- trans-THFs in high diastereoselectivity. A detailed mechanistic study using DFT calculation reveals details of the ligand-exchange step, suggesting an inner-sphere syn attack to form the 2,5- trans stereochemistry as the most likely pathway, excluding the previous cation radical intermediate. The formation of a Co-C intermediate is suggested on the basis of the homolytic cleavage to give the previously proposed free carbon radical intermediate.

• Publication year

  2018

• Venue

  Journal of Organic Chemistry

• Publication date

  2018-06-07

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1021/acs.joc.8b00575PMID 29878776
• 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.

• Fragment-Based Discovery of 2-Aminoquinazolin-4(3H)-ones As Novel Class Nonpeptidomimetic Inhibitors of the Plasmepsins I, II, and IV.

  2016cited by this paper
• Sodium amalgam mediated desulfonylative reduction of α-functionalized β-ketosulfones

  2016cited by this paper
• Cobalt-catalyzed oxidative cyclization of gem-disubstituted conjugated alkenols

  2016cited by this paper
• Concise total syntheses of amphidinolides C and F.

  2015cited by this paper
• Intramolecular Hydroalkoxylation of Unactivated Alkenes Using Silane-Iodine Catalytic System.

  2015cited by this paper
• Mechanistic insights into cobalt(ii/iii)-catalyzed C–H oxidation: a combined theoretical and experimental study

  2015cited by this paper
• Development of Enantioselective Palladium-Catalyzed Alkene Carboalkoxylation Reactions for the Synthesis of Tetrahydrofurans.

  2015cited by this paper
• Zinc-mediated CH-activation of tetrahydrofuran under mild conditions for the regioselective addition to aryl-propiolates.

  2014cited by this paper
• Enantioselective Synthesis of Tetrahydrofuran Derivatives by Sequential Henry Reaction and Iodocyclization of γ,δ‐Unsaturated Alcohols

  2014cited by this paper
• Stereoselective synthesis of side chain-functionalized tetrahydropyrans from 5-hexenols

  2014cited by this paper
• Alkene isomerisation catalysed by a ruthenium PNN pincer complex.

  2014cited by this paper
• A new poly(propylene imine) dendron as potential convenient building-block in the construction of multifunctional systems

  2013cited by this paper
• Syntheses of the C1-C14 and C15-C25 fragments of amphidinolide C.

  2013cited by this paper
• Direct functionalization of tetrahydrofuran and 1,4-dioxane: nickel-catalyzed oxidative C(sp3)-H arylation.

  2013cited by this paper
• Pd(0)-catalyzed alkene oxy- and aminoalkynylation with aliphatic bromoacetylenes.

  2013cited by this paper
• Tetrahydrofuran-containing macrolides: a fascinating gift from the deep sea.

  2013cited by this paper
• A General Synthesis of Bis‐α‐acyloxy‐1,4‐ and ‐1,5‐diketones Through Catalytic Oxidative Opening of Acylated THF and THP Diols

  2013cited by this paper
• Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

  2013cited by this paper
• Asymmetric Intramolecular Oxa-Michael Reactions to Tetrahydrofurans/2H-Pyrans Catalyzed by Primary–Secondary Diamines

  2013cited by this paper
• An aerobic oxidation/homolytic substitution-cascade for stereoselective methylsulfanyl-cyclization of 4-pentenols.

  2013cited by this paper
• Stereoselective synthesis of cis-2,5-disubstituted THFs: application to adjacent bis-THF cores of Annonaceous acetogenins.

  2012cited by this paper
• Total synthesis of (-)-goniotrionin.

  2012cited by this paper
• Investigating the arenyl-diene double [3 + 2] photocycloaddition reaction.

  2011cited by this paper
• Asymmetric catalytic cycloetherification mediated by bifunctional organocatalysts.

  2011cited by this paper
• How molecular oxygen binds to bis[trifluoroacetylacetonato(-1)]cobalt(II)--ab initio and density functional theory studies.

  2011cited by this paper
• The rate-determining step is dead. Long live the rate-determining state!

  2011cited by this paper
• Effect of the damping function in dispersion corrected density functional theory

  2011cited by this paper
• How to conceptualize catalytic cycles? The energetic span model.

  2011cited by this paper
• A general strategy for the stereocontrolled preparation of diverse 8- and 9-membered Laurencia-type bromoethers.

  2011cited by this paper
• Functionalized tetrahydrofurans from alkenols and olefins/alkynes via aerobic oxidation-radical addition cascades.

  2011cited by this paper
• Highly diastereoselective Pd-catalyzed carboetherification reactions of acyclic internal alkenes. Stereoselective synthesis of polysubstituted tetrahydrofurans.

  2010cited by this paper
• Cobalt-catalyzed aerobic oxidation of (E)- and (Z)-bishomoallylic alcohols

  2009cited by this paper
• Increased yields and simplified purification with a second-generation cobalt catalyst for the oxidative formation of trans-THF rings.

  2009cited by this paper
• Synthesis and first X-ray structures of cobalt(II) and cobalt(III) complexes bearing 2,4-dioxo-alkanoic acid dialkylamide ligands

  2009cited by this paper
• Reductive and brominative termination of alkenol cyclization in aerobic cobalt-catalyzed reactions.

  2009cited by this paper
• NHC-catalyzed ring expansion of oxacycloalkane-2-carboxaldehydes: a versatile synthesis of lactones.

  2009cited by this paper
• Multicatalytic synthesis of complex tetrahydrofurans involving bismuth(III) triflate catalyzed intramolecular hydroalkoxylation of unactivated olefins.

  2009cited by this paper
• Diastereoselective synthesis of 2,5-disubstituted tetrahydrofurans

  2009cited by this paper
• Amphidinolides and Its Related Macrolides from Marine Dinoflagellates

  2008cited by this paper
• Electronic Supporting Information for : Activation of Molecular Oxygen and its Use in Stereoselective Tetrahydrofuran-Syntheses from δ , ε-Unsaturated Alcohols

  2008cited by this paper
• Stereoselective synthesis of (+)-IKD-8344

  2007cited by this paper
• Total syntheses of ipomoeassin B and E.

  2007cited by this paper
• Recent Advances in the Stereoselective Synthesis of Tetrahydrofurans.

  2007cited by this paper
• Copper-catalyzed asymmetric [4+1] cycloadditions of enones with diazo compounds to form dihydrofurans.

  2007cited by this paper
• First total synthesis and structural reassignment of (-)-aplysiallene.

  2007cited by this paper
• Acetogenins from Annonaceae: recent progress in isolation, synthesis and mechanisms of action.

  2005cited by this paper
• Synthesis of unsaturated amino alcohols through unexpectedly selective Ru-catalyzed cross-metathesis reactions.

  2005cited by this paper
• Palladium-catalyzed synthesis of tetrahydrofurans from gamma-hydroxy terminal alkenes: scope, limitations, and stereoselectivity.

  2005cited by this paper
• Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy.

  2005cited by this paper
• Ruthenium-catalyzed olefin metathesis double-bond isomerization sequence.

  2004cited by this paper
• Catalytic Asymmetric C−H Activation of Alkanes and Tetrahydrofuran

  2000cited by this paper
• Grignard Reagent/Borohydride Combinations Alkylation/Reduction of Esters

  2000cited by this paper
• A Convenient Method for the Stereoselective Preparation of trans-2-Hydroxymethyltetrahydrofurans by the Oxidative Cyclization of 5-Hydroxy-1-alkenes with Molecular Oxygen Catalyzed by Cobalt(II) Complex

  1990cited by this paper
• Density-functional exchange-energy approximation with correct asymptotic behavior.

  1988cited by this paper
• Density-functional approximation for the correlation energy of the inhomogeneous electron gas.

  1986cited by this paper
• Cobalt(III)-catalyzed trifluoroacetoxylation of benzene

  1986cited by this paper
• Cobalt(III) trifluoroacetate: An electron transfer oxidant

  1973cited by this paper

• Base-Promoted Cobalt-Catalyzed Regio- and Enantioselective para-Friedel-Crafts Alkylation of Aniline Derivatives.

  2021cites this paper
• Cobalt-Catalyzed Chemoselective Transfer Hydrogenative Cyclization Cascade of Enone-Tethered Aldehydes.

  2021cites this paper
• Radical Reactions

  2021cites this paper
• Synthesis of 3-Carbonyl Trisubstituted Furans via Pd-Catalyzed Aerobic Cycloisomerization Reaction: Development and Mechanistic Studies.

  2021cites this paper
• Cobalt-Catalyzed Hartung-Mukaiyama Cyclization of γ-Hydroxy Olefins: Stereocontrolled Synthesis of the Tetrahydrofuran Moiety of Amphidinolide N.

  2021cites this paper
• Development and application of Mukaiyama oxidative cyclization for the synthesis of substituted tetrahydrofuran cores

  2020cites this paper
• Diastereoselective Synthesis of 2,3,4-Trisubstituted Tetrahydrofurans via Thermally Reactive 1,5-Diene-tert-butyl Carbonates.

  2020cites this paper
• Chagosensine: A Riddle Wrapped in a Mystery Inside an Enigma

  2020cites this paper
• FeCl3-catalyzed C-3 functionalization of imidazo[1,2-a]pyridines with diazoacetonitrile under oxidant- and ligand-free conditions

  2020cites this paper
• Total synthesis and complete configurational assignment of amphirionin-2

  2020cites this paper
• Copper-Catalyzed Oxydifluoroalkylation of Hydroxyl-Containing Alkenes.

  2019cites this paper
• Synthesis of the non-adjacent bis(tetrahydrofuran) core of squamostanin C by silicon-tethered, size-selective triple ring-closing metathesis

  2019cites this paper
• Synthesis of 2,5-trans-Tetrahydrofuran-2-ylacetonitriles

  2018cites this paper