HOTf-Catalyzed, Solvent-Free Oxyarylation of Ynol Ethers and Thioethers.

A novel HOTf-catalyzed oxyarylation of ynol ethers and thioethers has been realized with aryl sulfoxides as the oxyarylating reagents, providing α-arylated esters or thioesters in good to excellent yields. Notably, all atoms of the starting materials were incorporated in the product (100% atom economy) and the reaction proceeded under very mild conditions. It was found that the reaction can be ran under air and that the best yields are obtained under solvent-free conditions.

[1]  L. Veiros,et al.  Brønsted Acid-Mediated Hydrative Arylation of Unactivated Alkynes. , 2016, Chemistry.

[2]  Thomas G Minehan,et al.  A Single-Flask Synthesis of α-Alkylidene and α-Benzylidene Lactones from Ethoxyacetylene, Epoxides/Oxetanes, and Carbonyl Compounds. , 2016, Tetrahedron letters.

[3]  Song-Lin Zhang,et al.  C−C Activation by Retro-Aldol Reaction of Two β‑Hydroxy Carbonyl Compounds: Synergy with Pd-Catalyzed Cross-Coupling To Access Mono-α-arylated Ketones and Esters. , 2016, The Journal of organic chemistry.

[4]  Ze Tan,et al.  A rapid and selective synthesis of α,α-fluorohalo esters via fluorohalogenative or difluorinative hydration of ynol ethers. , 2015, Chemical communications.

[5]  Zhiqian Wang,et al.  The carbonyl group tuned electron-deficient phosphorus ligands and their application in Rhodium catalyzed arylation to aldehydes , 2015 .

[6]  P. Holland,et al.  Rapid, Regioconvergent, Solvent-Free Alkene Hydrosilylation with a Cobalt Catalyst. , 2015, Journal of the American Chemical Society.

[7]  Gangguo Zhu,et al.  Construction of 1-Naphthols via Benzannulation Based on the Reaction of Aryl tert-Butyl Ynol Ethers with Ynamides or Ynol Ethers. , 2015, The Journal of organic chemistry.

[8]  Alexander M. Spokoyny,et al.  Organometallic Palladium Reagents for Cysteine Bioconjugation , 2015, Nature.

[9]  Zigang Li,et al.  Catalytic Ring Expansion of Cyclic Hemiaminals for the Synthesis of Medium-Ring Lactams. , 2015, Angewandte Chemie.

[10]  P. Davies,et al.  Regioselective functionalisation of dibenzothiophenes through gold-catalysed intermolecular alkyne oxyarylation. , 2015, Organic & biomolecular chemistry.

[11]  Nozomi Saito,et al.  Nickel-promoted highly regioselective carboxylation of aryl ynol ether and its application to the synthesis of chiral β-aryloxypropionic acid derivatives. , 2015, Chemistry, an Asian journal.

[12]  Nathaniel H. Park,et al.  Design of New Ligands for the Palladium-Catalyzed Arylation of α-Branched Secondary Amines. , 2015, Angewandte Chemie.

[13]  T. Donohoe,et al.  Palladium-catalyzed α-arylation of carbonyls in the de novo synthesis of aromatic heterocycles , 2015, Organic & biomolecular chemistry.

[14]  R. Kant,et al.  Palladium-catalyzed regio- and stereoselective cross-addition of terminal alkynes to ynol ethers and synthesis of 1,4-enyn-3-ones. , 2015, Angewandte Chemie.

[15]  D. Procter,et al.  Sulfoxide-Directed Metal-Free ortho-Propargylation of Aromatics and Heteroaromatics , 2015, Chemistry.

[16]  S. Buchwald,et al.  Rational Ligand Design for the Arylation of Hindered Primary Amines Guided by Reaction Progress Kinetic Analysis , 2015, Journal of the American Chemical Society.

[17]  R. Gleiter,et al.  Dimerization of two alkyne units: model studies, intermediate trapping experiments, and kinetic studies. , 2015, Journal of the American Chemical Society.

[18]  K. Takasu,et al.  Development of a Brønsted acid-promoted arene-ynamide cyclization toward the total syntheses of marinoquinolines A and C and aplidiopsamine A. , 2015, The Journal of organic chemistry.

[19]  Pingfan Li,et al.  Sulfur mediated allylic C-H alkylation of tri- and disubstituted olefins. , 2014, Organic letters.

[20]  J. Hartwig,et al.  Pd-Catalyzed α-Arylation of Trimethylsilyl Enolates of α,α-Difluoroacetamides , 2014, Journal of the American Chemical Society.

[21]  D. Enders,et al.  Combining Silver Catalysis and Organocatalysis: A Sequential Michael Addition/Hydroalkoxylation One-Pot Approach to Annulated Coumarins , 2014, Organic letters.

[22]  Lan-Gui Xie,et al.  A Brønsted acid catalyzed redox arylation. , 2014, Angewandte Chemie.

[23]  J. Marrot,et al.  Keteniminium ion-initiated cascade cationic polycyclization. , 2014, Journal of the American Chemical Society.

[24]  Laura L. Anderson,et al.  Synthesis of 1,4-enamino ketones by [3,3]-rearrangements of dialkenylhydroxylamines. , 2014, Organic letters.

[25]  C. Farés,et al.  Chemoselective intermolecular α-arylation of amides. , 2014, Angewandte Chemie.

[26]  Gangguo Zhu,et al.  Palladium-catalyzed hydroarylation, hydroalkenylation, and hydrobenzylation of ynol ethers with organohalides: A regio- and stereoselective entry to α,β- and β,β-disubstituted alkenyl ethers. , 2014, The Journal of organic chemistry.

[27]  Guochen Jia,et al.  Iridium-catalyzed intermolecular azide-alkyne cycloaddition of internal thioalkynes under mild conditions. , 2014, Angewandte Chemie.

[28]  N. Maulide,et al.  Electrophilic rearrangements of chiral amides: a traceless asymmetric α-allylation. , 2013, Journal of the American Chemical Society.

[29]  D. Ess,et al.  Aerobic, transition-metal-free, direct, and regiospecific mono-α-arylation of ketones: synthesis and mechanism by DFT calculations. , 2013, Journal of the American Chemical Society.

[30]  David K. Leahy,et al.  Development of a scalable palladium-catalyzed α-arylation process for the synthesis of a CGRP antagonist , 2013 .

[31]  Liming Zhang,et al.  [3,3]-Sigmatropic rearrangement versus carbene formation in gold-catalyzed transformations of alkynyl aryl sulfoxides: mechanistic studies and expanded reaction scope. , 2013, Journal of the American Chemical Society.

[32]  C. Farés,et al.  Sulfur(IV)-mediated transformations: from ylide transfer to metal-free arylation of carbonyl compounds. , 2013, Journal of the American Chemical Society.

[33]  D. Procter,et al.  Nucleophilic ortho-propargylation of aryl sulfoxides: an interrupted Pummerer/allenyl thio-Claisen rearrangement sequence. , 2013, Angewandte Chemie.

[34]  Xiaoyi Chen,et al.  An operationally simple approach to (E)-α-halo vinyl sulfides and their applications for accessing stereodefined trisubstituted alkenes. , 2013, Organic & biomolecular chemistry.

[35]  Malcolm P. Huestis,et al.  Cyanide anion as a leaving group in nucleophilic aromatic substitution: synthesis of quaternary centers at azine heterocycles. , 2013, The Journal of organic chemistry.

[36]  Jean Rodriguez,et al.  Transition-metal-free α-arylation of β-keto amides via an interrupted insertion reaction of arynes. , 2012, Organic letters.

[37]  S. Mhaske,et al.  Transition-metal-free C-arylation at room temperature by arynes. , 2012, Organic letters.

[38]  G. Evano,et al.  Copper-Mediated Selective Cross-Coupling of 1,1-Dibromo-1-alkenes and Heteronucleophiles: Development of General Routes to Heterosubstituted Alkynes and Alkenes , 2012 .

[39]  C. Bolm,et al.  Transition-metal-free synthesis of oxindoles by potassium tert-butoxide-promoted intramolecular α-arylation. , 2012, Organic letters.

[40]  G. Evano,et al.  Copper-catalyzed coupling of 1,1-dibromo-1-alkenes with phenols: a general, modular, and efficient synthesis of ynol ethers, bromo enol ethers, and ketene acetals. , 2012, Organic letters.

[41]  Linfeng Hu,et al.  A one‐pot synthesis of alkynyl sulfides from terminal alkynes , 2012 .

[42]  D. Procter,et al.  Nucleophilic ortho allylation of aryl and heteroaryl sulfoxides. , 2011, Organic letters.

[43]  Alice E. Williamson,et al.  Enantioselective α-arylation of N-acyloxazolidinones with copper(II)-bisoxazoline catalysts and diaryliodonium salts. , 2011, Journal of the American Chemical Society.

[44]  D. MacMillan,et al.  Enantioselective α-arylation of carbonyls via Cu(I)-bisoxazoline catalysis. , 2011, Journal of the American Chemical Society.

[45]  D. MacMillan,et al.  Enantioselective α-arylation of aldehydes via the productive merger of iodonium salts and organocatalysis. , 2011, Journal of the American Chemical Society.

[46]  Yang Yang,et al.  A concise synthesis of paucifloral F and related indanone analogues via palladium-catalyzed α-arylation. , 2011, The Journal of organic chemistry.

[47]  P. Norrby,et al.  Alpha-arylation by rearrangement: on the reaction of enolates with diaryliodonium salts. , 2010, Chemistry.

[48]  M. Mąkosza.  Nucleophilic substitution of hydrogen in electron-deficient arenes, a general process of great practical value. , 2010, Chemical Society reviews.

[49]  S. Martin,et al.  Concise total synthesis of (+/-)-lycopladine A. , 2010, Organic letters.

[50]  B. Stoltz,et al.  Regioselective reactions of highly substituted arynes. , 2010, Organic letters.

[51]  B. Olofsson,et al.  Diaryliodonium salts: a journey from obscurity to fame. , 2009, Angewandte Chemie.

[52]  A. Lledós,et al.  Gold(I)-catalyzed intermolecular oxyarylation of alkynes: unexpected regiochemistry in the alkylation of arenes. , 2009, Organic letters.

[53]  C. Frizzo,et al.  Solvent-free heterocyclic synthesis. , 2009, Chemical reviews.

[54]  Jin‐Heng Li,et al.  Selective synthesis of o-acylbenzylphosphonates by insertion reactions of arynes into beta-ketophosphonates. , 2009, The Journal of organic chemistry.

[55]  P. Baran,et al.  A simple method for the direct arylation of indoles , 2009 .

[56]  P. Stang,et al.  Chemistry of polyvalent iodine. , 2008, Chemical reviews.

[57]  M. Fagnoni,et al.  Aryl Cation Chemistry as an Emerging Versatile Tool for Metal-Free Arylations , 2008 .

[58]  L. Bieber,et al.  Copper-Catalyzed Regioselective Coupling of Allylic Halides and Alkynes Promoted by Weak Inorganic Bases. , 2007 .

[59]  L. Brown,et al.  Welwistatin support studies: expansion and limitation of aryllead(IV) coupling reactions. , 2007, The Journal of organic chemistry.

[60]  Liming Zhang,et al.  Gold-catalyzed intramolecular redox reaction of sulfinyl alkynes: efficient generation of alpha-oxo gold carbenoids and application in insertion into R--CO bonds. , 2007, Angewandte Chemie.

[61]  N. Shapiro,et al.  Rearrangement of alkynyl sulfoxides catalyzed by gold(I) complexes. , 2007, Journal of the American Chemical Society.

[62]  M. Hiersemann,et al.  The Claisen Rearrangement , 2007 .

[63]  Yeeman K. Ramtohul,et al.  Direct C-Arylation of β-Enamino Esters and Ketones with Arynes , 2007 .

[64]  V. Aggarwal,et al.  Enantioselective alpha-arylation of cyclohexanones with diaryl iodonium salts: application to the synthesis of (-)-epibatidine. , 2005, Angewandte Chemie.

[65]  B. Stoltz,et al.  The direct acyl-alkylation of arynes. , 2005, Journal of the American Chemical Society.

[66]  Y. Matano,et al.  A new, efficient method for direct α-alkenylation of β-dicarbonyl compounds and phenols using alkenyltriarylbismuthonium salts , 2004 .

[67]  Ana M. Martin Castro,et al.  Claisen rearrangement over the past nine decades. , 2004 .

[68]  Mayumi Kimura,et al.  A practical procedure for the synthesis of multifunctional aldehydes through the Fukuyama reduction and elucidation of the reaction site and mechanism , 2004 .

[69]  Phillip K. Koech,et al.  Phosphine catalyzed alpha-arylation of enones and enals using hypervalent bismuth reagents: regiospecific enolate arylation via nucleophilic catalysis. , 2004, Journal of the American Chemical Society.

[70]  J. Hartwig,et al.  Palladium-Catalyzed α-Arylation of Esters and Amides under More Neutral Conditions , 2003 .

[71]  K. Maruoka,et al.  Fluorotetraphenylbismuth: a new reagent for efficient regioselective alpha-phenylation of carbonyl compounds. , 2003, Journal of the American Chemical Society.

[72]  J. Konopelski,et al.  Aryllead(IV) reagents in synthesis: formation of the C11 quaternary center of N-methylwelwitindolinone C isothiocyanate. , 2001, Organic letters.

[73]  Gregory I. Elliott,et al.  Arylation with Organolead and Organobismuth Reagents , 2001 .

[74]  J. Šrogl,et al.  Thiol Ester−Boronic Acid Coupling. A Mechanistically Unprecedented and General Ketone Synthesis , 2000 .

[75]  John F. Hartwig,et al.  Unusual in Situ Ligand Modification to Generate a Catalyst for Room Temperature Aromatic C−O Bond Formation , 2000 .

[76]  M. Olmstead,et al.  Diastereoselectivity in the Formation of Quaternary Centers with Aryllead(IV) Tricarboxylates , 1999 .

[77]  N. Rosen,et al.  Total Synthesis of Spirotryprostatin A, Leading to the Discovery of Some Biologically Promising Analogues , 1999 .

[78]  J. Morgan,et al.  α-Arylation of ketones by aryllead triacetates. Effect of methyland phenyl substitution at the α position , 1997 .

[79]  H. Suginome,et al.  Photoinduced molecular transformations. 158. A total synthesis of (.+-.)-methyl piperitol: An unsymmetrically substituted 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignan , 1995 .

[80]  J. Finet.  Arylation reactions with organobismuth reagents , 1989 .

[81]  D. Barton,et al.  Bismuth(V) reagents in organic synthesis , 1987 .

[82]  T Y Shen,et al.  Perspectives in nonsteroidal anti-inflammatory agents. , 1972, Angewandte Chemie.

[83]  L. Claisen.  Über Umlagerung von Phenol-allyläthern in C-Allyl-phenole , 1912 .