Silver-Catalyzed Enantioselective Carbon Dioxide Incorporation into Bispropargylic Alcohols

Yoshida, Shosuke; Fukui, Kosuke; Kikuchi, Satoshi; Yamada, Tohru

doi:10.1021/ja1007118

Cited by 142 publications

(64 citation statements)

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“…[16] Indeed,s ilver compounds in combination with organic bases, for example, DBU (2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine) or nitrogencontaining ligands, effectively catalyzed the carboxylative cyclization of propargyl alcohols with CO 2 . [17] Furthermore, N-heterocyclic olefins can also be used as an robust organocatalyst, rendering the reactionp roceed under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

Ag^I/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Song

Lang

et al. 2017

ChemPhysChem

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Chemical valorization of CO2 to access various value‐added compounds has been a long‐term and challenging objective from the viewpoint of sustainable chemistry. Herein, a one‐pot three‐component reaction of terminal propargyl alcohols, CO2, and 2‐aminoethanols was developed for the synthesis of 2‐oxazolidinones and an equal amount of α‐hydroxyl ketones promoted by Ag2O/TMG (1,1,3,3‐tetramethylguanidine) with a TON (turnover number) of up to 1260. By addition of terminal propargyl alcohol, the thermodynamic disadvantage of the conventional 2‐aminoethanol/CO2 coupling was ameliorated. Mechanistic investigations including control experiments, DFT calculation, kinetic and NMR studies suggest that the reaction proceeds through a cascade pathway and TMG could activate propargyl alcohol and 2‐aminoethanol through the formation of hydrogen bonds and also activate CO2.

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Section: Introductionmentioning

confidence: 99%

Ag^I/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Song

Lang

et al. 2017

ChemPhysChem

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“…(Scheme 11). 50 The configuration appears to be determined by the conformation of the cyclization transition state (TS), but note that CO2 does not become bound to the chiral centre.…”

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confidence: 99%

Enantioselective Incorporation of CO₂: Status and Potential

et al. 2017

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CO2 is a promising and sustainable carbon feedstock for organic synthesis. New catalytic protocols for efficient incorporation of CO2 into organic molecules are continuously reported. However, little progress has been made in the enantioselective conversion of CO2 to form enantioenriched molecules. In order to allow CO2 to become a versatile carbon source in academia, and in the fine chemical and pharmaceutical industries, the development of enantioselective approaches is essential. Here we discuss general strategies for CO2 activation and for generation of enantioenriched molecules, alongside selected examples of reactions involving asymmetric incorporation of CO2. Main product classes considered are carboxylic acids and derivatives (C-2 CO2 bonds), and carbonates, carbamates, and polycarbonates (C-OCO bonds). Similarities to asymmetric hydrogenation are discussed, and some strategies for developing novel enantioselective CO2 reactions are outlined.

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“…11 We also describe the asymmetric incorporation of CO 2 into bispropargylic alcohol catalyzed by a chiral silver salt derived from silver acetate and Schiff base ligand to give the corresponding chiral cyclic carbonate in good to excellent yields with high enantioselectivity. 12 The reaction mechanism postulated by a computational approach, the determination of the absolute configuration of the optically active cyclic carbonate using VCD spectroscopy and X-ray analysis, and the application of an optically active cyclic carbonate for aminolysis, is also reported.…”

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confidence: 99%

Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives

Kikuchi¹,

Yoshida²,

Sugawara³

et al. 2011

Bulletin of the Chemical Society of Japan

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118

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A silver/DBU catalyst system was developed for the effective synthesis of cyclic carbonate and oxazolidinone from the reaction of CO 2 with propargylic alcohols and propargylic amines, respectively, in high yields under mild conditions. It was found that the [3,3]-sigmatropic MeyerSchuster-type rearrangement of the propargylic alcohol was mediated by CO 2 in DMF to afford the corresponding ¡,¢-unsaturated carbonyl compounds in high yields. The silver salt combined with the chiral Schiff base ligand could be applied to enantioselective chemical CO 2 incorporation into various bispropargylic alcohols to produce the corresponding cyclic carbonate in high yields with high enantioselectivity. The absolute configuration was determined by VCD spectroscopy as well as by X-ray analysis. These products were found to be active for the aminolysis reaction to afford the corresponding carbamate derivatives in high yields without any loss of optical purity.An enormous amount of energy has been generated by the oxidation of hydrocarbons in order to make our life comfortable and convenient while generating an enormous amount of CO 2 worldwide.1 Because the most oxidized form of the carbon derivatives is much less reactive, its application to organic synthesis has been considered to be one of the most challenging research topics. As well as the chemical fixation of CO 2 , much effort has been made to utilize CO 2 as an attractive C1 feedstock for organic synthesis due to its ubiquitous, abundant, and nontoxic properties, however due to its lower reactivity, harsh reaction conditions are required to activate and incorporate CO 2 into organic compounds.2 It is necessary to develop a mild reaction system including catalysts to efficiently capture CO 2 into a wide variety of substrates, especially fine-chemicals. Various synthetic reactions of CO 2 have been reported. Typically enol derivatives, 3 Grignard reagents, 4 and alkyllithium compounds 5 readily react with CO 2 to afford the corresponding carboxylic acids, though a stoichiometric amount of a strong nucleophile is employed. Transition-metals, such as nickel, 6 rhodium, 7 palladium, 8 copper, 2e,9 and gold, 2e can catalyze the reaction of CO 2 to produce the corresponding carboxylic acid and lactone derivatives. However, it is required to prepare in advance reactants containing a boron, halogen moiety, etc., and the scope and applicability are limited.It was recently found that a catalytic amount of a silver salt as a ³-Lewis acid to activate an alkyne combined with the use of DBU is an efficient catalyst system for the reaction of CO 2 with propargylic derivatives. We now report that a silver salt/DBU combination catalyzes the reaction of CO 2 with propargylic alcohols 10a and propargylic amines 10b to produce the corresponding cyclic carbonates and oxazolidinones in good to excellent yields, respectively. We also describe that a MeyerSchuster-type rearrangement is mediated by CO 2 in the presence of a catalytic amount of silver methanesulfonate and a base to afford the corre...

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Silver-Catalyzed Enantioselective Carbon Dioxide Incorporation into Bispropargylic Alcohols

Abstract: The combined catalyst system of silver acetate with a chiral Schiff base ligand achieved asymmetric carbon dioxide incorporation into bispropargylic alcohols with desymmetrization to afford the corresponding cyclic carbonates with good-to-excellent enantiomeric excesses.

Cited by 142 publications

References 26 publications

Ag^I/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Ag^I/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Enantioselective Incorporation of CO₂: Status and Potential

Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives

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Silver-Catalyzed Enantioselective Carbon Dioxide Incorporation into Bispropargylic Alcohols

Abstract: The combined catalyst system of silver acetate with a chiral Schiff base ligand achieved asymmetric carbon dioxide incorporation into bispropargylic alcohols with desymmetrization to afford the corresponding cyclic carbonates with good-to-excellent enantiomeric excesses.

Cited by 142 publications

References 26 publications

AgI/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

AgI/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Enantioselective Incorporation of CO2: Status and Potential

Silver-Catalyzed Carbon Dioxide Incorporation and Rearrangement on Propargylic Derivatives

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Resources

About

Ag^I/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Ag^I/TMG‐Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2‐Aminoethanols to 2‐Oxazolidinones

Enantioselective Incorporation of CO₂: Status and Potential