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Title: 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.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. New York University, 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)
Contributing Org.:
New York University
OSTI Identifier:
1657174
Alternate Identifier(s):
OSTI ID: 1481798
Grant/Contract Number:  
FG02-03ER15459
Resource Type:
Journal Article: 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},
url = {https://www.osti.gov/biblio/1657174}, journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 70,
volume = 24,
place = {United States},
year = {2018},
month = {10}
}

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Cited by: 2 works
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