Shell Cross-Linked Micelles as Nanoreactors for Enantioselective Three-Step Tandem Catalysis
Abstract
We describe functionalized amphiphilic poly(2-oxazoline)-based triblock copolymers that assemble into shell cross-linked micelles (SCMs). These micelles permit for the site isolation of three incompatible catalysts through compartmentalization, thereby enabling three-step non-orthogonal tandem processes in one pot. In particular, the acid catalyzed ketal hydrolysis to prochiral ketones proceeds in the hydrophilic corona, followed by the Rh-catalyzed asymmetric transfer hydrogenation to enantio-enriched alcohols in the cross-linked shell, and nucleophilic base-catalyzed acylation in the hydrophobic core. The catalysts are positioned in close proximity on a single micelle support to take advantage of intramicellar substrate diffusion, yet are sufficiently spaced apart from each other in physically distinct microenvironments. These compartmentalized micelles are substrate selective and, on a basic level, mimic compartmentalized catalytic architectures found in nature.
- Publication Date:
- Research Org.:
- Georgia Institute of Technology, Atlanta, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- New York University
- OSTI Identifier:
- 1657174
- Alternate Identifier(s):
- OSTI ID: 1481798
- Grant/Contract Number:
- FG02-03ER15459
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Volume: 24; Journal Issue: 70; Journal ID: ISSN 0947-6539
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Kuepfert, Michael, Cohen, Aaron E., Cullen, Olivia, and Weck, Marcus. Shell Cross-Linked Micelles as Nanoreactors for Enantioselective Three-Step Tandem Catalysis. United States: N. p., 2018.
Web. doi:10.1002/chem.201804956.
Kuepfert, Michael, Cohen, Aaron E., Cullen, Olivia, & Weck, Marcus. Shell Cross-Linked Micelles as Nanoreactors for Enantioselective Three-Step Tandem Catalysis. United States. https://doi.org/10.1002/chem.201804956
Kuepfert, Michael, Cohen, Aaron E., Cullen, Olivia, and Weck, Marcus. Mon .
"Shell Cross-Linked Micelles as Nanoreactors for Enantioselective Three-Step Tandem Catalysis". United States. https://doi.org/10.1002/chem.201804956. https://www.osti.gov/servlets/purl/1657174.
@article{osti_1657174,
title = {Shell Cross-Linked Micelles as Nanoreactors for Enantioselective Three-Step Tandem Catalysis},
author = {Kuepfert, Michael and Cohen, Aaron E. and Cullen, Olivia and Weck, Marcus},
abstractNote = {We describe functionalized amphiphilic poly(2-oxazoline)-based triblock copolymers that assemble into shell cross-linked micelles (SCMs). These micelles permit for the site isolation of three incompatible catalysts through compartmentalization, thereby enabling three-step non-orthogonal tandem processes in one pot. In particular, the acid catalyzed ketal hydrolysis to prochiral ketones proceeds in the hydrophilic corona, followed by the Rh-catalyzed asymmetric transfer hydrogenation to enantio-enriched alcohols in the cross-linked shell, and nucleophilic base-catalyzed acylation in the hydrophobic core. The catalysts are positioned in close proximity on a single micelle support to take advantage of intramicellar substrate diffusion, yet are sufficiently spaced apart from each other in physically distinct microenvironments. These compartmentalized micelles are substrate selective and, on a basic level, mimic compartmentalized catalytic architectures found in nature.},
doi = {10.1002/chem.201804956},
journal = {Chemistry - A European Journal},
number = 70,
volume = 24,
place = {United States},
year = {Mon Oct 01 00:00:00 EDT 2018},
month = {Mon Oct 01 00:00:00 EDT 2018}
}
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Works referencing / citing this record:
Tandem Catalysis with Antagonistic Catalysts Compartmentalized in the Dispersed and Continuous Phases of a Pickering Emulsion
journal, April 2019
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