Ruthenium-catalyzed dimerization of propiolates: a simple route to α-pyrones.

A ruthenium-catalyzed regioselective intermolecular multistep homo- and heterodimerization of substituted propiolates providing α-pyrone-5-carboxylates and α-pyrone-6-carboxylates is described. The synthetic utilities of α-pyrone derivatives are shown. The proposed mechanism is strongly supported by experimental evidence.

[1]  T. Roisnel,et al.  One-step synthesis of 1-halo-1,3-butadienes via ruthenium-catalysed hydrohalogenative dimerisation of alkynes. , 2012, Chemical communications.

[2]  M. Jeganmohan,et al.  Regioselective synthesis of isocoumarins by ruthenium-catalyzed aerobic oxidative cyclization of aromatic acids with alkynes. , 2012, Chemical communications.

[3]  S. Schreiber,et al.  Syntheses of α-Pyrones Using Gold-Catalyzed Coupling Reactions , 2011, Organic letters.

[4]  George A. Kraus,et al.  Aromatics from pyrones: para-substituted alkyl benzoates from alkenes, coumalic acid and methyl coumalate , 2011 .

[5]  C. Cho,et al.  Intramolecular imino Diels-Alder approach to the synthesis of the aspidosperma alkaloid from 3,5-dibromo-2-pyrone. , 2010, Organic letters.

[6]  M. Shindo,et al.  Stereoselective synthesis of (E)-2-en-4-ynoic acids with ynolates: catalytic conversion to tetronic acids and 2-pyrones. , 2009, Organic letters.

[7]  A. Goel,et al.  Natural and synthetic 2H-pyran-2-ones and their versatility in organic synthesis☆ , 2009 .

[8]  K. Hirano,et al.  Synthesis of functionalized alpha-pyrone and butenolide derivatives by rhodium-catalyzed oxidative coupling of substituted acrylic acids with alkynes and alkenes. , 2009, The Journal of organic chemistry.

[9]  Jongmin Park,et al.  Diastereoselective synthesis of polycyclic acetal-fused pyrano[3,2-c]pyran-5(2H)-one derivatives. , 2009, The Journal of organic chemistry.

[10]  K. Takai,et al.  Rhenium- and manganese-catalyzed insertion of acetylenes into beta-keto esters: synthesis of 2-pyranones. , 2008, Chemical communications.

[11]  Chien‐Hong Cheng,et al.  Cobalt- and nickel-catalyzed regio- and stereoselective reductive coupling of alkynes, allenes, and alkenes with alkenes. , 2008, Chemistry.

[12]  Chien‐Hung Yeh,et al.  Regioselective synthesis of gamma-amino esters, nitriles, sulfones, and pyrrolidinones by nickel-catalyzed reductive coupling of aldimines and activated alkenes. , 2008, Angewandte Chemie.

[13]  S. Schreiber,et al.  Complex α-Pyrones Synthesized by a Gold-Catalyzed Coupling Reaction† , 2007 .

[14]  Chien‐Hong Cheng,et al.  New catalytic reactions of oxa- and azabicyclic alkenes. , 2007, Accounts of chemical research.

[15]  T. Fukuyama,et al.  Ru-catalyzed intermolecular [3+2+1] cycloaddition of alpha,beta-unsaturated ketones with silylacetylenes and carbon monoxide leading to alpha-pyrones. , 2007, Organic letters.

[16]  C. Bruneau,et al.  Metal vinylidenes and allenylidenes in catalysis: applications in anti-Markovnikov additions to terminal alkynes and alkene metathesis. , 2006, Angewandte Chemie.

[17]  M. Krische,et al.  Highly enantioselective direct reductive coupling of conjugated alkynes and alpha-ketoesters via rhodium-catalyzed asymmetric hydrogenation. , 2006, Journal of the American Chemical Society.

[18]  B. Trost,et al.  Ruthenium-catalyzed reactions--a treasure trove of atom-economic transformations. , 2005, Angewandte Chemie.

[19]  I. Fairlamb,et al.  2-Pyrone natural products and mimetics: isolation, characterisation and biological activity. , 2005, Natural product reports.

[20]  J. Montgomery.  Nickel-catalyzed reductive cyclizations and couplings. , 2004, Angewandte Chemie.

[21]  M. J. Uddin,et al.  Design, synthesis, and structure-activity relationship studies of 3,4,6-triphenylpyran-2-ones as selective cyclooxygenase-2 inhibitors. , 2004, Journal of medicinal chemistry.

[22]  Hye‐Young Jang,et al.  Catalytic C-C bond formation via capture of hydrogenation intermediates. , 2004, Accounts of chemical research.

[23]  O. Eisenstein,et al.  Biscarbene-ruthenium complexes in catalysis: novel stereoselective synthesis of (1E,3E)-1,4-disubstituted-1,3-dienes via head-to-head coupling of terminal alkynes and addition of carboxylic acids. , 2003, Journal of the American Chemical Society.

[24]  L. Toupet,et al.  Ruthenium-Catalyzed One-Step Transformation of Propargylic Alcohols into Alkylidene Cyclobutenes: X-ray Characterization of an Ru(η3 -cyclobutenyl) Intermediate. , 2001, Angewandte Chemie.

[25]  B. Trost,et al.  Non-metathesis ruthenium-catalyzed C-C bond formation. , 2001, Chemical reviews.

[26]  Chien‐Hong Cheng,et al.  Nickel‐Catalyzed Highly Regio‐ and Stereoselective Cyclization of Oxanorbornenes with Alkyl Propiolates: A Novel Method for the Synthesis of Benzocoumarin Derivatives , 2001 .

[27]  S. Ikeda,et al.  Nickel-catalyzed intermolecular domino reactions. , 2000, Accounts of chemical research.

[28]  J. Montgomery,et al.  Nickel-catalyzed cyclizations, couplings, and cycloadditions involving three reactive components. , 2000, Accounts of chemical research.

[29]  J. Parrain,et al.  Palladium-catalysed annulation reaction of allenyltins with β-iodo vinylic acids: selective synthesis of α-pyrones , 2000 .

[30]  R. Larock,et al.  Synthesis of Isocoumarins and alpha-Pyrones via Palladium-Catalyzed Annulation of Internal Alkynes. , 1999, The Journal of organic chemistry.

[31]  J. Fishpaugh,et al.  A versatile synthesis of .alpha.-pyrones , 1983 .

[32]  K. G. Migliorese,et al.  Skipped diynes. IV. Diacetylenic ketone reactions , 1974 .

[33]  K. K. Chen,et al.  Pharmacology and toxicology of toad venom. , 1967, Journal of pharmaceutical sciences.

[34]  C. Harris,et al.  Carboxylation of β-Dicarbonyl Compounds through Dicarbanions. Cyclizations to 4-Hydroxy-2-pyrones1 , 1966 .

[35]  R. H. Wiley,et al.  2-Pyrones. IX. 2-Pyrone-6-carboxylic Acid and its Derivatives , 1954 .

[36]  C. L. Bickel.  The Addition of Malonic Esters to an Acetylenic Ketone , 1950 .