Silver(I)-Catalyzed Three-Component Reaction of Propargylic Alcohols, Carbon Dioxide and Monohydric Alcohols: Thermodynamically Feasible Access to β-Oxopropyl Carbonates.

A silver(I)-catalyzed three-component reaction of propargylic alcohols, CO2 , and monohydric alcohols was successfully developed for the synthesis of β-oxopropyl carbonates. As such, a series of β-oxopropyl carbonates were exclusively produced in excellent yields (up to 98 %), even under atmospheric pressure of CO2 . The silver catalyst works efficiently for both the carboxylative cyclization of propargylic alcohols with CO2 and subsequent transesterification of α-alkylidene cyclic carbonates with monohydric alcohols; thus this tandem process performs smoothly under mild conditions. This work provides a versatile and thermodynamically favorable approach to dissymmetric dialkyl carbonates.

[1]  B. Han,et al.  Zinc(II)-catalyzed reactions of carbon dioxide and propargylic alcohols to carbonates at room temperature , 2016 .

[2]  Liang‐Nian He,et al.  Silver(I)-Catalyzed Synthesis of β-Oxopropylcarbamates from Propargylic Alcohols and CO2 Surrogate: A Gas-Free Process. , 2015, ChemSusChem.

[3]  Bing Yan,et al.  Recent advances in dialkyl carbonates synthesis and applications. , 2015, Chemical Society reviews.

[4]  Liang‐Nian He,et al.  Bifunctional silver(I) complex-catalyzed CO2 conversion at ambient conditions: synthesis of α-methylene cyclic carbonates and derivatives. , 2015, ChemSusChem.

[5]  M. Beller,et al.  Using carbon dioxide as a building block in organic synthesis , 2015, Nature Communications.

[6]  John-Paul Jones,et al.  Recycling of carbon dioxide to methanol and derived products - closing the loop. , 2014, Chemical Society reviews.

[7]  T. Ema,et al.  Recent progress in catalytic conversions of carbon dioxide , 2014 .

[8]  M. Chen,et al.  Gold-catalyzed oxidative reactions of propargylic carbonates involving 1,2-carbonate migration: stereoselective synthesis of functionalized alkenes. , 2014, The Journal of organic chemistry.

[9]  Hui Zhou,et al.  Alkoxide-functionalized imidazolium betaines for CO2 activation and catalytic transformation , 2014 .

[10]  M. Aresta,et al.  Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2. , 2014, Chemical reviews.

[11]  J. Yue,et al.  Organic carbonates from natural sources. , 2014, Chemical reviews.

[12]  Mingyuan He,et al.  Grüne Kohlenstoffwissenschaft: eine wissenschaftliche Grundlage für das Verknüpfen von Verarbeitung, Nutzung und Recycling der Kohlenstoffressourcen , 2013 .

[13]  Yuhan Sun,et al.  Green carbon science: scientific basis for integrating carbon resource processing, utilization, and recycling. , 2013, Angewandte Chemie.

[14]  Arjan W. Kleij,et al.  Stereoselective synthesis with carbon dioxide , 2013 .

[15]  S. Caillol,et al.  Synthesis and applications of unsaturated cyclocarbonates , 2013 .

[16]  Huanfeng Jiang,et al.  Polystyrene‐Supported N‐Heterocyclic Carbene–Silver Complexes as Robust and Efficient Catalysts for the Reaction of Carbon Dioxide and Propargylic Alcohols , 2013 .

[17]  Guoping Xu,et al.  Interface engineering: Boosting the energy conversion efficiencies for nanostructured solar cells , 2012 .

[18]  Zhenzhen Yang,et al.  Carbon dioxide utilization with C–N bond formation: carbon dioxide capture and subsequent conversion , 2012 .

[19]  D. Darensbourg,et al.  Cobalt catalysts for the coupling of CO2 and epoxides to provide polycarbonates and cyclic carbonates. , 2012, Chemical Society reviews.

[20]  B. Gabriele,et al.  Effective Guanidine-Catalyzed Synthesis of Carbonate and Carbamate Derivatives from Propargyl Alcohols in Supercritical Carbon Dioxide , 2011 .

[21]  Masafumi Yamamoto,et al.  N-heterocyclic carbenes as efficient organocatalysts for CO2 fixation reactions. , 2009, Angewandte Chemie.

[22]  M. Willis,et al.  Direct catalytic diastereoselective Mannich reactions: the synthesis of protected α-hydroxy-β-aminoketones , 2009 .

[23]  T. Sakakura,et al.  The synthesis of organic carbonates from carbon dioxide. , 2009, Chemical communications.

[24]  Tohru Yamada,et al.  Silver‐Catalyzed Incorporation of Carbon Dioxide into Propargylic Alcohols , 2007 .

[25]  B. Trost,et al.  Enantioselective synthesis of alpha-tertiary hydroxyaldehydes by palladium-catalyzed asymmetric allylic alkylation of enolates. , 2007, Journal of the American Chemical Society.

[26]  Youquan Deng,et al.  Ionic liquid as an efficient promoting medium for fixation of CO2: clean synthesis of alpha-methylene cyclic carbonates from CO2 and propargyl alcohols catalyzed by metal salts under mild conditions. , 2004, The Journal of organic chemistry.

[27]  C. Bruneau,et al.  Stereoselective preparation of Z-trisubstituted alkylidene cyclic carbonates via palladium-catalyzed carboncarbon bond formation , 2000 .

[28]  S. Murai,et al.  Palladium-catalyzed reactions of ketone .alpha.-carbonates with norbornenes. An unusual cyclopropanation , 1993 .

[29]  C. Bruneau,et al.  Direct access to β-oxopropyl carbonates from bulky alcohols , 1993 .

[30]  C. Bruneau,et al.  A New Route to Functional α-Enones via Prop-2-ynyl Alcohol Derivatives and Carbonates , 1992 .

[31]  T. Hosokawa,et al.  Palladium(II)-catalysed oxidation of carbon–carbon double bonds of allylic compounds with molecular oxygen; regioselective formation of aldehydes , 1991 .

[32]  C. Bruneau,et al.  Functional carbonates: cyclic α-methylene and β-oxopropyl carbonates from prop-2-ynyl alcohol derivatives and CO2 , 1991 .

[33]  R. A. Olofson,et al.  A simple synthesis of 1-(1,3-butadienyl) carbonates and carbamates , 1990 .

[34]  C. Bruneau,et al.  Phosphine catalysed synthesis of unsaturated cyclic carbonates from carbon dioxide and propargylic alcohols , 1989 .