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Title: Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations

Abstract

This contribution introduces poly(2-oxazoline)-based shell cross-linked micelles (SCMs) as nanoreactors to realize one-pot redox-driven deracemizations of secondary alcohols in aqueous media. TEMPO and Rh-TsDPEN moieties are spatially positioned into the hydro-philic corona and the hydrophobic micelle core, respectively. TEMPO catalyzes the oxidation of racemic secondary alcohols into ketones while Rh-TsDPEN catalyzes the asymmetric transfer hydrogenation (ATH) of these ketones to afford enantioenriched secondary alco-hols. Both catalysts, the Rh-TsDPEN complex and TEMPO are incompatible with each other and the SCMs are designed to provide indispensable catalyst site-isolation. Kinetic studies show that the SCMs enhance the reactivity of the immobilized catalysts, compared to those for the unsupported analogs under the same reaction conditions. In conclusion, our nanoreactors can perform deracemizations on a broad range of secondary alcohol substrates and are reusable in a continuous manner while maintaining high activity.

Authors:
 [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. New York University, NY (United States)
  2. Columbia University, New York, NY (United States)
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:
1657171
Grant/Contract Number:  
FG02-03ER15459
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cross-linked micelle; poly(2-oxazoline); deracemization; TEMPO oxidation; asymmetric transfer hydrogenation; oxidation reactions; catalysts; redox reaction; oxidation; nanodevices

Citation Formats

Qu, Peiyuan, Kuepfert, Michael, Jockusch, Steffen, and Weck, Marcus. Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations. United States: N. p., 2019. Web. doi:10.1021/acscatal.8b04667.
Qu, Peiyuan, Kuepfert, Michael, Jockusch, Steffen, & Weck, Marcus. Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations. United States. https://doi.org/10.1021/acscatal.8b04667
Qu, Peiyuan, Kuepfert, Michael, Jockusch, Steffen, and Weck, Marcus. 2019. "Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations". United States. https://doi.org/10.1021/acscatal.8b04667. https://www.osti.gov/servlets/purl/1657171.
@article{osti_1657171,
title = {Compartmentalized Nanoreactors for One-Pot Redox-Driven Transformations},
author = {Qu, Peiyuan and Kuepfert, Michael and Jockusch, Steffen and Weck, Marcus},
abstractNote = {This contribution introduces poly(2-oxazoline)-based shell cross-linked micelles (SCMs) as nanoreactors to realize one-pot redox-driven deracemizations of secondary alcohols in aqueous media. TEMPO and Rh-TsDPEN moieties are spatially positioned into the hydro-philic corona and the hydrophobic micelle core, respectively. TEMPO catalyzes the oxidation of racemic secondary alcohols into ketones while Rh-TsDPEN catalyzes the asymmetric transfer hydrogenation (ATH) of these ketones to afford enantioenriched secondary alco-hols. Both catalysts, the Rh-TsDPEN complex and TEMPO are incompatible with each other and the SCMs are designed to provide indispensable catalyst site-isolation. Kinetic studies show that the SCMs enhance the reactivity of the immobilized catalysts, compared to those for the unsupported analogs under the same reaction conditions. In conclusion, our nanoreactors can perform deracemizations on a broad range of secondary alcohol substrates and are reusable in a continuous manner while maintaining high activity.},
doi = {10.1021/acscatal.8b04667},
url = {https://www.osti.gov/biblio/1657171}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 4,
volume = 9,
place = {United States},
year = {Thu Feb 21 00:00:00 EST 2019},
month = {Thu Feb 21 00:00:00 EST 2019}
}

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Cited by: 48 works
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Works referencing / citing this record:

Fighting Deactivation: Classical and Emerging Strategies for Efficient Stabilization of Molecular Electrocatalysts
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