Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor
Abstract
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.
- Authors:
-
[2];
[1]
- Computational NanoBio Technology Laboratory, School of Materials Science and Engineering, Georgia Institute of Technology, 771 Ferst Drive NW, Atlanta, Georgia 30332-0245, United States
- Molecular Design Institute and Department of Chemistry, New York University, New York, New York 10003, United States
- Department of Nanomechatronics Engineering, Pusan National University, Miryang 50463, Korea
- Publication Date:
- Research Org.:
- Georgia Institute of Technology, Atlanta, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2205530
- Alternate Identifier(s):
- OSTI ID: 2222374
- Grant/Contract Number:
- FG02-03ER15459
- Resource Type:
- Published Article
- Journal Name:
- Journal of Physical Chemistry. B
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry. B Journal Volume: 127 Journal Issue: 46; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Addition reactions; Aldol reactions; Catalysts; Molecules; Solvents
Citation Formats
Cho, Jinwon, Weck, Marcus, Hwang, Sungu, and Jang, Seung Soon. Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor. United States: N. p., 2023.
Web. doi:10.1021/acs.jpcb.3c05858.
Cho, Jinwon, Weck, Marcus, Hwang, Sungu, & Jang, Seung Soon. Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor. United States. https://doi.org/10.1021/acs.jpcb.3c05858
Cho, Jinwon, Weck, Marcus, Hwang, Sungu, and Jang, Seung Soon. Mon .
"Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor". United States. https://doi.org/10.1021/acs.jpcb.3c05858.
@article{osti_2205530,
title = {Multiscale Modeling Approach for the Aldol Addition Reaction in Multicompartment Micelle-Based Nanoreactor},
author = {Cho, Jinwon and Weck, Marcus and Hwang, Sungu and Jang, Seung Soon},
abstractNote = {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.},
doi = {10.1021/acs.jpcb.3c05858},
journal = {Journal of Physical Chemistry. B},
number = 46,
volume = 127,
place = {United States},
year = {Mon Nov 13 00:00:00 EST 2023},
month = {Mon Nov 13 00:00:00 EST 2023}
}
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