A Simple and Versatile Method for the Formation of Acetals/Ketals Using Trace Conventional Acids

Dong, Jian-Lian; Yu, Li‐Si‐Han; Xie, Jian‐Hua

doi:10.1021/acsomega.8b00159

Cited by 78 publications

(59 citation statements)

References 67 publications

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“…Thus, as expected, the corresponding acetal products 2 were obtained in excellent yields up to the fifth cycle at room temperature. It is noteworthy that the same reaction under mineral acid catalysis was failed to resue . These results suggest that the present acetalization does not follow the classical (mineral) acid catalysed pathway.…”

Section: Methodsmentioning

confidence: 91%

“…Notably, when we reduce the catalyst loading from 1 mol % to 0.01 mol % the reaction preceded smoothly and afforded the desired product 2 a in excellent yield (Table , entries 11–12). A control experiment with 2‐methyl 2‐butene (radical and chloride quencher) showed that this reaction does not follow the classical mineral acid catalytic pathway (Table , entry 15). Indeed, increasing the temperature does not have any influence on product formation (Table , entry 14).…”

Section: Methodsmentioning

confidence: 98%

See 1 more Smart Citation

Nickel‐Catalyzed Chemoselective Acetalization of Aldehydes With Alcohols under Neutral Conditions

Subaramanian

Landge

Mondal

et al. 2019

Chemistry An Asian Journal

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Am olecularly defined Ni II -complex catalyzing the chemoselective acetalization of aldehydes with alcohols under neutralc onditions is reported. The reactioni s general, efficient and showedawide substrate scope (including aliphatic aldehydes)a sw ell as excellent functional group tolerance. Reusability of the present nickel catalyst is also demonstrated.Development of new catalytic approaches, in particular,c atalysts based on cheap,e arth-abundant, non-precious metalsf or sustainable chemical synthesis is the key motivation in contemporary science. The carbonyl compounds such as aldehydes and ketones are the most significant functional groups in organic synthesis owing to their ubiquitous, andv ersatile reactivity.I nt he multi-stepo rganic transformations,ag reen protocol for the protection or maskingo fc arbonyl compounds that operate under neutralc onditions is highly required. In this regard, acetalization reaction using widespread alcohols hasa ttracted much interest. Acetals serve as an excellent protective group of carbonyl compounds [1] as well as they found various applicationsi nt he synthesis of chiral auxiliaries, steroids, flavoring agents, and pharmaceutical moieties. [2][3][4] In general, acetalization involves the condensation of carbonyl compounds with alcoholic substrates in the presence of Brçnsted/Lewis acid, mineral acid, or base catalysts. [5] However, these protocols often requireatoxic orthoformate as an alcohol source (for acetalization). Indeed,t hese approaches have inherentl imitations such as handling of corrosivea cid catalyst, high temperature, longer reaction time, and limited substrates scope. In recent times, variousc atalytic methods including or-ganocatalysts, [6a-f] photo-redox catalysts, [7a-c] and heterogeneous catalysts [8a-c] and transition-metal catalysis [9] have been reportedi nr eplacement of highly acidic conditions. Nevertheless, these methods require high catalystl oading and harsh reaction conditions.Recently,L yons et al. reported the acetalization of aldehydes in the presence of tropylium salt as organo-Lewisa cidc atalyst using triethyl orthoformate as alcohol source.T his methodr equiresh eating condition, longerr eactiont ime, and an excess amount of Na 2 SO 4 as the dehydrating agent for the cyclic acetalization. [10] Hudnall and co-workers reported antimony(V) catalyzed acetalization of aldehydesi nt he presence of as toichiometrica mount of either triethoxymethane or triethoxysilane, and the products can be purified by distillation processw hich limits the scope of this protocol for thermally stable substrates. [11] However, both of these methods require as toichiometric amount of toxic triethylo rthoformates and triethylo rthoformate/silicate, respectively.T hus, it would be of interest to develop as imple and eco-benign catalystt hat works under neutral and mild reaction conditions and avoid the use of toxic orthoformates. Here, we report am olecularly defined nickel(II) complex catalyzed acetalization of aldehydes using widespread alcohols. The re...

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Section: Methodsmentioning

confidence: 91%

Section: Methodsmentioning

confidence: 98%

Nickel‐Catalyzed Chemoselective Acetalization of Aldehydes With Alcohols under Neutral Conditions

Subaramanian

Landge

Mondal

et al. 2019

Chemistry An Asian Journal

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“…The ketalization of carbonyl compounds with diols is a common transformation (Figure 12), which is typically implemented to ensure chemoselective transformation upon protection of aldehydes or ketones within the frame of complex organic synthesis, [197] though it also concerns the production of fuel additives and the manufacturing of building blocks toward high added‐value. Ketals have also a promising future in the polymer industry as biodegradable smart polymers [198] .…”

Section: Staple Reactions Toward the Upgrading Of Bio‐based Vicinal P...mentioning

confidence: 99%

Perspectives for the Upgrading of Bio‐Based Vicinal Diols within the Developing European Bioeconomy

Muzyka

Monbaliu

2022

ChemSusChem

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The previous decade has witnessed a drastic increase of European incentives aimed at pushing forward the transition from an exclusively petro‐based economy toward a strong and homogeneous bio‐based economy. Since 2012, numerous programs have been developed to stimulate and promote research and innovation relying on sustainable and renewable resources. Terrestrial biomass is a virtually infinite reservoir of biomacromolecules, the biorefining of which provides platform molecules of low complexity yet with tremendous industrial potential. Among such bio‐based platform molecules, polyols and, more specifically, molecules featuring vicinal diols have gained tremendous interest and have stimulated an increasing research effort from the chemistry and chemical engineering communities. This Review revolves around the most promising process conditions and technologies reported since 2012 that specifically target bio‐based vicinal diols and promote their transformation into value‐added molecules of wide industrial interest, such as olefins, epoxides, cyclic carbonates, and ketals.

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“…Además, se han llevado a cabo estudios experimentales (Trifoi et al, 2016), (Ferreira et al, 2019); trabajos teóricos (Azofra et al, 2012) sobre síntesis de hemiacetales y estudios donde dicha reacción puede ser catalizada por medio de una base (Funderburk et al, 1978), (Grabowski et al, 2018) de un ácido de Brönsted (Dong et al, 2018), (Yang et al, 2005), de un ácido de…”

Section: Introductionunclassified

Estudio teórico de la síntesis de hemiacetales catalizada por ácidos de Lewis

Caglieri

Macaño

2021

Jour. Bol. Cien.

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Se llevó a cabo un estudio teórico de la síntesis de acetaldehído metilhemiacetal, benzaldehído metilhemiacetal, 4-metil benzaldehído metilhemiacetal y 4-nitro benzaldehído metilhemiacetal, comparando la reactividad de los aldehídos frente a la reacción con metanol, catalizada por iones metálicos: Zn2+; Co2+, Mn2+; Cu2+ y Ni2+, a través del análisis de los intermediarios de reacción correspondientes e indicando la influencia del anillo aromático y de los iones metálicos en la velocidad de dicha reacción. Las energías de activación y las de los intermediarios de reacción se calcularon con el método Universal Force Field (UFF). Los valores obtenidos se compararon con datos de la literatura. La obtención de hemiacetales, además de su utilidad dentro de la industria química, es una reacción usada frecuentemente en síntesis orgánica, al proporcionar un medio eficiente y económico para proteger el grupo carbonilo en un proceso sintético. El acetaldehído presentó la mayor reactividad frente a la reacción de síntesis de hemiacetales en todos los casos, el anillo aromático disminuyó la velocidad de reacción y el Zn2+ resultó ser el ion metálico más reactivo, reportando los valores más bajos de energía.

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A Simple and Versatile Method for the Formation of Acetals/Ketals Using Trace Conventional Acids

Cited by 78 publications

References 67 publications

Nickel‐Catalyzed Chemoselective Acetalization of Aldehydes With Alcohols under Neutral Conditions

Nickel‐Catalyzed Chemoselective Acetalization of Aldehydes With Alcohols under Neutral Conditions

Perspectives for the Upgrading of Bio‐Based Vicinal Diols within the Developing European Bioeconomy

Estudio teórico de la síntesis de hemiacetales catalizada por ácidos de Lewis

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