Metal-Catalyzed Acyl Transfer Reactions of Enol Esters:  Role of Y5(OiPr)13O and (thd)2Y(OiPr) as Transesterification Catalysts

and, Mei-Huey Lin; RajanBabu, T. V.

doi:10.1021/ol0057131

Cited by 80 publications

(35 citation statements)

References 22 publications

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“…Other oxometallic species catalyze nucleophilic acyl substitution reactions with protic nucleophiles. Examples are TiO(acetylacetonate)2, vanadyl dichloride VOCl2(THF)n, [48] and Y5(O-i-Pr)13O [76], all being water-tolerant catalysts. …”

Section: Amphoteric Compounds Are Good Catalysts For Acyl Transfersmentioning

confidence: 99%

“…[318]. A few years later, Mizuhara and co-workers described the catalytic activity of natural thiamine (76) which, in the form of its pyrophosphate (77), is the coenzyme for a number of important biochemical reactions, including decarboxylation of pyruvate into acetaldehyde, the transketolase-catalyzed reaction and the oxidative decarboxylation of pyruvic acid into active acetate [319]. In 1958, Breslow presented the mechanism shown in Scheme 47 for the thiazolium ion-catalyzed benzoin condensation.…”

Section: Benzoin Condensation: Umpolung Of Aldehydesmentioning

confidence: 99%

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Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

et al. 2016

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Catalysis fulfills the promise that high-yielding chemical transformations will require little energy and produce no toxic waste. This message is carried by the study of the evolution of molecular catalysis of some of the most important reactions in organic chemistry. After reviewing the conceptual underpinnings of catalysis, we discuss the applications of different catalysts according to the mechanism of the reactions that they catalyze, including acyl group transfers, nucleophilic additions and substitutions, and C-C bond forming reactions that employ umpolung by nucleophilic additions to C=O and C=C double bonds. We highlight the utility of a broad range of organocatalysts other than compounds based on proline, the cinchona alkaloids and binaphthyls, which have been abundantly reviewed elsewhere. The focus is on organocatalysts, although a few examples employing metal complexes and enzymes are also included due to their significance. Classical Brønsted acids have evolved into electrophilic hands, the fingers of which are hydrogen donors (like enzymes) or other electrophilic moieties. Classical Lewis base catalysts have evolved into tridimensional, chiral nucleophiles that are N-(e.g., tertiary amines), P-(e.g., tertiary phosphines) and C-nucleophiles (e.g., N-heterocyclic carbenes). Many efficient organocatalysts bear electrophilic and nucleophilic moieties that interact simultaneously or not with both the electrophilic and nucleophilic reactants. A detailed understanding of the reaction mechanisms permits the design of better catalysts. Their construction represents a molecular science in itself, suggesting that sooner or later chemists will not only imitate Nature but be able to catalyze a much wider range of reactions with high chemo-, regio-, stereo-and enantioselectivity. Man-made organocatalysts are much smaller, cheaper and more stable than enzymes.

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Section: Amphoteric Compounds Are Good Catalysts For Acyl Transfersmentioning

confidence: 99%

Section: Benzoin Condensation: Umpolung Of Aldehydesmentioning

confidence: 99%

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

et al. 2016

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“…Acylation of amino alcohols [60][61][62][63]. Treatment with a strong acylating agent under acidic conditions will also result in clean esterification.…”

Section: Alcohols With Additional Nucleophilic Groupsmentioning

confidence: 99%

The Acylation of Heteroatoms

Dörwald

2004

Side Reactions in Organic Synthesis

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“…7 They may also lead to formation of side products and deterioration of primary products during the prolonged reaction times. 8 Nolan's group have paid plenty of attentions on N-heterocyclic carbene (NHC) catalyzed transesterification and shown that NHCs act as efficient organocatalysts to mediate this transformation.…”

Section: Introductionmentioning

confidence: 99%

Significant Heterogeneous Carbonate Salt Catalyzed Acetylation of Alcohols via a Transesterification Process with Carbonate Salt-activated Alcohol ¹ H NMR Evidence

Xiong

Zhang

2011

Chin. J. Chem.

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Heterogeneous carbonate salt catalyzed acetylation of alcohols via a transesterification process has been developed. Various esters are furnished up to 97% yield. Established procedure is simple and air-tolerant with readily available reagents. Ethyl acetate and isobutyl acetate are used as not only acetylating agents, but also reaction solvents in transesterification. Aliphatic linear alcohols, allylic alcohols and benzyl alcohols show high reactivities in the presence of 1 or 5 mol% Cs 2 CO 3 at 125 ℃. Cesium carbonate can be recycled by pumping liquid phase out of reactor after reaction. During four cycle runs for reaction of 2-phenylethanol and ethyl acetate, high yields of phenethyl acetate are provided (＞60% yield). Based on experiments and 1 H NMR investigation, bifunctional catalysis is proposed, alcohol activated by carbonate ion is confirmed, and higher activity of catalytic amount than stoichiometric cesium carbonate is interpreted.

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Metal-Catalyzed Acyl Transfer Reactions of Enol Esters: Role of Y₅(OⁱPr)₁₃O and (thd)₂Y(OⁱPr) as Transesterification Catalysts

Cited by 80 publications

References 22 publications

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

The Acylation of Heteroatoms

Significant Heterogeneous Carbonate Salt Catalyzed Acetylation of Alcohols via a Transesterification Process with Carbonate Salt-activated Alcohol ¹ H NMR Evidence

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Metal-Catalyzed Acyl Transfer Reactions of Enol Esters: Role of Y5(OiPr)13O and (thd)2Y(OiPr) as Transesterification Catalysts

Cited by 80 publications

References 22 publications

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

Organocatalysis: Fundamentals and Comparisons to Metal and Enzyme Catalysis

The Acylation of Heteroatoms

Significant Heterogeneous Carbonate Salt Catalyzed Acetylation of Alcohols via a Transesterification Process with Carbonate Salt-activated Alcohol 1 H NMR Evidence

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Product

Resources

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Metal-Catalyzed Acyl Transfer Reactions of Enol Esters: Role of Y₅(OⁱPr)₁₃O and (thd)₂Y(OⁱPr) as Transesterification Catalysts

Significant Heterogeneous Carbonate Salt Catalyzed Acetylation of Alcohols via a Transesterification Process with Carbonate Salt-activated Alcohol ¹ H NMR Evidence