Synthesis of Alkali Metal Carboxylates and Carboxylic Acids Using “Wet” and “Anhydrous” Alkali Metal Hydroxides

Krief, Alain; Kremer, Adrian

doi:10.1021/cr9003506

Cited by 13 publications

(11 citation statements)

References 288 publications

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“…Desilylation using TBAF was accompanied by hydrolysis of the C-3 ester to give the known diester 27 in 67% yield. Finally, hydrolysis of the remaining more-hindered esters using anhydrous KOH gave (−)-6,7-dideoxysqualestatin H5 2 possessing spectral data in complete agreement with that previously reported …”

supporting

confidence: 89%

Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

et al. 2017

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An asymmetric synthesis of (-)-6,7-dideoxysqualestatin H5 is reported. Key features of the synthesis include the following: (1) highly diastereoselective n-alkylation of a tartrate acetonide enolate and subsequent oxidation-hydrolysis to provide an asymmetric entry to a β-hydroxy-α-ketoester motif; (2) facilitation of Rh(II)-catalyzed cyclic carbonyl ylide formation-cycloaddition by co-generation of keto and diazo functionality through ozonolysis of an unsaturated hydrazone; and (3) stereoretentive Ni-catalyzed Csp-Csp cross-electrophile coupling between tricarboxylate core and unsaturated side chain to complete the natural product.

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supporting

confidence: 89%

Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

et al. 2017

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“…It is worth to note that complex 3 even can catalyze the ROP of 1000 equiv of rac -lactide in the presence of 1 equiv of BnOH, affording desirable high molecular weight of 107 kg/mol, acceptable polydispersity of Đ = 1.37, and not bad P m value of 0.78 at 0 °C (Table , entry 17). This phenomenon can change our prejudice of sodium complexes in the synthesis of high molecular weight polylactide because alkali complexes usually suffer from serious side reactions of cyclization, transesterification, and even epimerization. ,− It also indicates this kind of sodium/potassium complex can be comparable to that of known aluminum, rare-earth-metal, and zinc catalysis systems. In addition, this system also can hold high isoselectivity.…”

Section: Resultsmentioning

confidence: 99%

Suppressing Cyclic Polymerization for Isoselective Synthesis of High-Molecular-Weight Linear Polylactide Catalyzed by Sodium/Potassium Sulfonamidate Complexes

et al. 2016

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A new sodium/potassium crown ether complex system with a series of bichelating sulfonamides as ligands was developed for the ring-opening polymerization (ROP) of rac-lactide. In this system, the side reaction of cyclic polymerization can be suppressed very well because of very different ROP rates initiated by BnOH and sulfonamide anion. The synthesis of high molecular weight linear polylactide with molecular weight high up to 107 kg/mol was successful. The best isoselectivity also can reach to a high value of P m = 0.84. The NMR analysis of the reaction mixture of rac-lactide and complex 3 together with kinetic studies suggests the mechanism of ROP in the absence of alcohol is a coordination–insertion mechanism. After addition of BnOH, the ROP rate can increase remarkably due to the cooperation interaction of alcohol and complex 3.

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“…7 This route is more sustainable than the currently used hydrolysis of alkynyl bromides and carbonylation of alkynes as well as the transformation of expensive alkynyl metals. 8,9 Silver (Ag)-based catalysts can efficiently catalyze this reaction, 10 as reported by the groups of Inoue, 11 Lu, 12,13 Gooßen, 14,15 Zhang, 16,17 He, 18 and Verpoort. 19,20 Yet, most of them are homogeneous Ag(I) complexes and salts, making it difficult for catalyst recovery and product separation.…”

Section: ■ Introductionmentioning

confidence: 85%

“…The catalytic conversion of carbon dioxide (CO 2 ) into chemicals is an emerging strategy in green organic synthesis, reducing CO 2 emissions while also supplementing the carbon demand of the chemical industry. − Only a few feasible catalytic processes have been developed for using CO 2 as a starting material, not least because CO 2 is thermodynamically and kinetically stable. , The insertion of CO 2 into terminal alkynes via carboxylation is one of the most straightforward routes for producing alkynyl carboxylic acids, which are key intermediates in the pharmaceutical and fine chemical sectors . This route is more sustainable than the currently used hydrolysis of alkynyl bromides and carbonylation of alkynes as well as the transformation of expensive alkynyl metals. , …”

Section: Introductionmentioning

confidence: 99%

Size-Controlled Growth of Silver Nanoparticles onto Functionalized Ordered Mesoporous Polymers for Efficient CO₂ Upgrading

Zhang

Mei

Huang

et al. 2019

ACS Appl. Mater. Interfaces

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Highly dispersed metallic silver nanoparticles (AgNPs) are promising heterogeneous catalysts for carboxylative coupling of terminal alkynes with CO2 under mild conditions. Yet, their size-controlled synthesis is very challenging because of the high surface energy. Here, we prepared a series of amino-functionalized ordered mesoporous polymers as hosts for anchoring AgNPs. Control experiments and computations showed that electron-rich amines were confined in mesochannels with varying electron density and steric hindrance, creating “localized active zones (LAZ)” to control the growth of AgNPs. The particle size of AgNPs grows along with the increased volume of LAZ around nitrogen species. We also revealed that the catalytic activity of Ag-based catalysts is size-dependent and increases with decreasing particle size. Building on these findings, we report a facile one-pot synthesis strategy for preparing an amine-incorporated ordered mesoporous polymer (NOMP) with a high specific surface area, small LAZ volume, and uniform amine sites with controllable loading. These features result in the formation of ultrasmall and monodispersed Ag nanoparticles. Remarkably, Ag@NOMP gave a quantitative target yield under the conditions of 1 atm CO2 pressure and 50 °C, showing superior catalytic activity in CO2 carboxylation compared to other mesoporous analogues.

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Synthesis of Alkali Metal Carboxylates and Carboxylic Acids Using “Wet” and “Anhydrous” Alkali Metal Hydroxides

Cited by 13 publications

References 288 publications

Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

Suppressing Cyclic Polymerization for Isoselective Synthesis of High-Molecular-Weight Linear Polylactide Catalyzed by Sodium/Potassium Sulfonamidate Complexes

Size-Controlled Growth of Silver Nanoparticles onto Functionalized Ordered Mesoporous Polymers for Efficient CO₂ Upgrading

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Synthesis of Alkali Metal Carboxylates and Carboxylic Acids Using “Wet” and “Anhydrous” Alkali Metal Hydroxides

Cited by 13 publications

References 288 publications

Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

Synthesis of (−)-6,7-Dideoxysqualestatin H5 by Carbonyl Ylide Cycloaddition–Rearrangement and Cross-electrophile Coupling

Suppressing Cyclic Polymerization for Isoselective Synthesis of High-Molecular-Weight Linear Polylactide Catalyzed by Sodium/Potassium Sulfonamidate Complexes

Size-Controlled Growth of Silver Nanoparticles onto Functionalized Ordered Mesoporous Polymers for Efficient CO2 Upgrading

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Size-Controlled Growth of Silver Nanoparticles onto Functionalized Ordered Mesoporous Polymers for Efficient CO₂ Upgrading