Scope and mechanism of the highly stereoselective metal-mediated domino aldol reactions of enolates with aldehydes

Çınar, Mehmet; Engelen, B.; Panthöfer, Martin; Deiseroth, Hans-Jörg; Schlirf, Jens; Schmittel, Michael

doi:10.3762/bjoc.12.80

Cited by 6 publications

(3 citation statements)

References 44 publications

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“…Density functional theory (DFT) calculations were performed using B3LYP density functional implemented in the Gaussian 09 (revision D.01) suit of package . B3LYP functional was chosen as this functional has been consistently found to provide reliable results in the theoretical study of aldol condensation reactions involving organic molecules . Correlation consistent cc‐pVDZ basis set was used for all the atoms.…”

Section: Methodsmentioning

confidence: 99%

“…[11] B3LYP functional was chosen as this functional has been consistently found to provide reliable results in the theoretical study of aldol condensation reactions involving organic molecules. [12][13][14][15][16][17] Correlation consistent cc-pVDZ basis set [18] was used for all the atoms. All the structures were optimized in water solvent, modeled by using SMD implicit solvation.…”

Section: Computational Detailsmentioning

confidence: 99%

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DFT investigations of the unusual reactivity of 2‐pyridinecarboxaldehyde in base‐catalyzed aldol reactions with acetophenone

Wachter

Rani

Zolfaghari

et al. 2020

J of Physical Organic Chem

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The aldol reaction is recognized as an archetypal method to form carbon‐carbon bonds. Base‐catalyzed aldol reactions of aryl aldehydes with aryl methyl ketones typically produce condensation products (chalcones). However, 2‐pyridinecarboxaldehye, 2‐quinolinecarboxaldehyde, and 2‐ and 3‐fluorobenzaldehyde undergo tandem aldol‐Michael reactions with aryl enolates to yield conjugate addition products. To elucidate the different reactivities of aldol products formed in the reactions of benzaldehyde and 2‐pyridinecarboxaldehyde with the sodium enolate of acetophenone, density functional theory (DFT) calculations were performed to compare the energies of conformational isomers of the intermediates formed in the reaction, the energies of the corresponding condensation products, and the kinetic barriers to dehydration and conjugate addition. Computational results support the formation of the trans isomer of the condensation product in base‐catalyzed aldol reactions of either benzaldehyde or 2‐pyridinecarboxaldehyde with acetophenone. The susceptibility of the condensation product to conjugate addition is determined to result from the lower LUMO energy of trans‐1‐phenyl‐3‐(2‐pyridinyl)‐2‐propen‐1‐one. Consequently, the kinetic barrier for conjugate addition of a second equivalent of enolate with the condensation product of 2‐pyridinecarboxaldehyde is found to be significantly lower. Similar results were obtained for the reactions of fluorobenzaldehydes with aryl enolates.

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Section: Methodsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

DFT investigations of the unusual reactivity of 2‐pyridinecarboxaldehyde in base‐catalyzed aldol reactions with acetophenone

Wachter

Rani

Zolfaghari

et al. 2020

J of Physical Organic Chem

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“… 15 – 17 ) As such, the protonation of the metal aldolates, furnishing racemic aldols with no diastereoselectivity, 15 , 16 ) was hardly expected to enable highly enantioselective catalysis without Tishchenko reduction. 18 ) Although the Mannich reaction approach serves as an alternative strategy to bestow α-chirality along with a newly fashioned carbon–carbon bond using aldehyde equivalents, it suffered from low enantioselectivity (Scheme 1 b). 19 , 20 )…”

Section: Introductionmentioning

confidence: 99%

Highly enantioselective hydroxymethylation of unmodified α-substituted aryl ketones in water

KITANOSONO,

KAWASE,

YAMASHITA

et al. 2023

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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Catalytic asymmetric direct-type aldol reactions of ketones with aldehydes are a perennial puzzle for organic chemists. Notwithstanding the emergence of a myriad of chiral catalysts to address the inherent reversibility of the aldol products, a general method to access acyclic α-chiral ketones from prochiral aryl ketones has remained an unmet synthetic challenge. The approach outlined herein is fundamentally different to that used in conventional catalysis, which typically commences with an α-proton abstraction by a Brønsted base. The use of a chiral 2,2′-bipyridine scandium complex enabled the hydroxymethylation of propiophenone to be run under base-free conditions, which avails effectual suppression of hydrolytic deactivation of the Lewis acid catalyst. Intriguingly, the use of water as a reaction medium had an overriding effect on the progress of the reaction. The sagacious selection of sodium dodecyl sulfate and lithium dodecyl sulfate as surfactants allowed a variety of propiophenone derivatives to react in a highly enantioselective manner.

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Recent Advances in Acid–Base and Solvation Properties of Metal Phenolates

Bastos

Machado

2017

Patai's Chemistry of Functional Groups

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This chapter is an update of a recent review on the acid–base chemistry and solvation properties of metal phenolates. After a brief introduction on the physicochemical properties of metal phenolates, the interaction between phenolate ligands and metal Lewis acids is discussed. Examples of solvent effects on the acid–base properties, structure, and chemical reactivity are presented. Furthermore, the interaction of multidentate phenolic ligands and metal cations is highlighted because of their relevance in transition‐metal coordination chemistry, catalyst development, metalloenzyme mimicry, cytotoxicity, and magnetic properties.

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Scope and mechanism of the highly stereoselective metal-mediated domino aldol reactions of enolates with aldehydes

Cited by 6 publications

References 44 publications

DFT investigations of the unusual reactivity of 2‐pyridinecarboxaldehyde in base‐catalyzed aldol reactions with acetophenone

DFT investigations of the unusual reactivity of 2‐pyridinecarboxaldehyde in base‐catalyzed aldol reactions with acetophenone

Highly enantioselective hydroxymethylation of unmodified α-substituted aryl ketones in water

Recent Advances in Acid–Base and Solvation Properties of Metal Phenolates

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