Enantiodivergent Aldol Condensation in the Presence of Aziridine/Acid/Water Systems

Pieczonka, Adam M.; Marciniak, Lena; Rachwalski, Michał; Leśniak, Stanisław

doi:10.3390/sym12060930

Cited by 4 publications

(2 citation statements)

References 37 publications

(52 reference statements)

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“…The presence of water molecules surrounding the AT and l -proline catalysts can significantly alter the reaction mechanism. As proposed by many theoretical studies, the involvement of water introduces new reaction pathways as water serves not only as a solvating agent but also as a proton transfer assistant, and thus influencing the overall reaction pathways and kinetics. − To evaluate the dual behaviors of water, we calculated the reaction kinetics in the presence of a single water molecule, as depicted in Figure . Unlike TS12 and TS1a , water in TS1a+H 2 O allows for proton transfer to the carbonyl oxygen of acetone, which requires E a = 41.2 kcal/mol for the reaction to proceed.…”

Section: Resultsmentioning

confidence: 99%

Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor

Cho,

Weck,

Hwang

et al. 2023

J. Phys. Chem. B

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Water has emerged as a versatile solvent for organic chemistry in recent years due to its abundance, low cost, and environmental friendliness. However, one of the most important reactions, the aldol reaction, in the presence of excess water exhibits low yields and poor enantioselectivities. In this regard, we have employed a multiscale modeling approach to investigate the aldol addition reaction catalyzed by L-proline in the hydrophobic compartment of multicompartment micelle (MCM) nanoreactor consisting of amphiphilic bottlebrush copolymer, which minimizes the water content at the reactive site. Through performing dissipative particle dynamics (DPD) simulation, it is found that the "clover-like" morphology of the MCM is formed from multiblock copolymer with a sequence of ethylene oxide-based hydrophilic blocks, styrene lipophilic blocks, L-proline catalyst blocks, and a pentafluorostyrene fluorophilic block in aqueous media. We find that the vicinity of the catalyst in the clover-like MCM has a low dielectric environment, which could facilitate the aldol addition reaction. Our DFT calculations demonstrate that the asymmetric aldol addition of L-proline-catalyzed acetone and 4-nitrobenzaldehyde is energetically more favorable under the low dielectric environment in MCM compared with other commonly used solvents such as DMSO, water, and vacuum condition.

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Section: Resultsmentioning

confidence: 99%

Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor

Cho,

Weck,

Hwang

et al. 2023

J. Phys. Chem. B

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“…It should be pointed out that the successful application of phosphinoyl-aziridines as organocatalysts in the asymmetric Michael [33] and Mannich reaction [34] was reported in our department. Based on our experience in the field of asymmetric catalysis [35][36][37] and continuing our studies on phosphorus-containing chiral aziridines [33,34], we have attempted the synthesis of chiral aziridine-phosphines. Their catalytic ability was then checked in the asymmetric Friedel-Crafts alkylation of indoles using β-nitrostyrene in the presence of a copper(I) triflate benzene complex.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Friedel–Crafts Alkylation of Indoles Catalyzed by Chiral Aziridine-Phosphines

et al. 2020

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Over the course of the present studies, a series of optically pure phosphines functionalized by chiral aziridines was synthesized in reasonable/good chemical yields. Their catalytic activity was checked in the enantioselective Friedel–Crafts alkylation of indoles by β-nitrostyrene in the presence of a copper(I) trifluoromethanesulfonate benzene complex. The corresponding Friedel–Crafts products were achieved efficiently in terms of chemical yield and enantioselectivity (up to 85% in some cases).

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Y(OTf)3-Salazin-Catalyzed Asymmetric Aldol Condensation

Wang,

Chen,

Yang

et al. 2024

Molecules

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The chiral aziridine-containing vicinal iminophenol tridentate ligands (named salazins) are a class of readily prepared chiral ligands from enantiopure aziridines and salicylaldehydes. Their scandium and yttrium triflate complexes show excellent reactivity and enantioselectivities in the catalytic asymmetric aldol condensation of electron-deficient aromatic aldehydes and ketones, including acetone and cycloalkanones. The stereoselectivity is rationalized to the strong π–stacking interaction between aromatic aldehydes and the vicinal iminophenol group in the chiral ligands.

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Enantiodivergent Aldol Condensation in the Presence of Aziridine/Acid/Water Systems

Cited by 4 publications

References 37 publications

Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor

Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor

Asymmetric Friedel–Crafts Alkylation of Indoles Catalyzed by Chiral Aziridine-Phosphines

Y(OTf)3-Salazin-Catalyzed Asymmetric Aldol Condensation

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