Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

Handle URI:
http://hdl.handle.net/10754/598162
Title:
Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst
Authors:
Thomas, Renee M.; Widger, Peter C. B.; Ahmed, Syud M.; Jeske, Ryan C.; Hirahata, Wataru; Lobkovsky, Emil B.; Coates, Geoffrey W.
Abstract:
A highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.
Citation:
Thomas RM, Widger PCB, Ahmed SM, Jeske RC, Hirahata W, et al. (2010) Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst. Journal of the American Chemical Society 132: 16520–16525. Available: http://dx.doi.org/10.1021/ja1058422.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
KAUST Grant Number:
KUS-C1-018-02
Issue Date:
24-Nov-2010
DOI:
10.1021/ja1058422
PubMed ID:
21043488
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
We thank the NSF (CHE-0809778), King Abdullah University of Science and Technology (KAUST; Award No. KUS-C1-018-02), and Sumitomo Chemicals for support. This research made use of the Cornell Center for Materials Research Shared Experimental Facilities supported through the NSF MRSEC program (DMR-0502404). R.M.T. acknowledges a Hunter Rawlings Cornell Presidential Research Scholarship. We thank Mr. Tom Mourey and Ms. Lisa Slater for GPC analysis of poly(1,1,1-trifluoro-2,3-epoxypropane) and Dr. Ivan Keresztes for assistance with the NMR analysis of 3.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorThomas, Renee M.en
dc.contributor.authorWidger, Peter C. B.en
dc.contributor.authorAhmed, Syud M.en
dc.contributor.authorJeske, Ryan C.en
dc.contributor.authorHirahata, Wataruen
dc.contributor.authorLobkovsky, Emil B.en
dc.contributor.authorCoates, Geoffrey W.en
dc.date.accessioned2016-02-25T13:13:52Zen
dc.date.available2016-02-25T13:13:52Zen
dc.date.issued2010-11-24en
dc.identifier.citationThomas RM, Widger PCB, Ahmed SM, Jeske RC, Hirahata W, et al. (2010) Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst. Journal of the American Chemical Society 132: 16520–16525. Available: http://dx.doi.org/10.1021/ja1058422.en
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.pmid21043488en
dc.identifier.doi10.1021/ja1058422en
dc.identifier.urihttp://hdl.handle.net/10754/598162en
dc.description.abstractA highly active enantiopure bimetallic cobalt complex was explored for the enantioselective polymerization of a variety of monosubstituted epoxides. The polymerizations were optimized for high rates and stereoselectivity, with s-factors (kfast/kslow) for most epoxides exceeding 50 and some exceeding 300, well above the threshold for preparative utility of enantiopure epoxides and isotactic polyethers. Values for mm triads of the resulting polymers are typically greater than 95%, with some even surpassing 98%. In addition, the use of a racemic catalyst allowed the preparation of isotactic polyethers in quantitative yields. The thermal properties of these isotactic polyethers are presented, with many polymers exhibiting high T m values. This is the first report of the rapid synthesis of a broad range of highly isotactic polyethers via the enantioselective polymerization of racemic epoxides. © 2010 American Chemical Society.en
dc.description.sponsorshipWe thank the NSF (CHE-0809778), King Abdullah University of Science and Technology (KAUST; Award No. KUS-C1-018-02), and Sumitomo Chemicals for support. This research made use of the Cornell Center for Materials Research Shared Experimental Facilities supported through the NSF MRSEC program (DMR-0502404). R.M.T. acknowledges a Hunter Rawlings Cornell Presidential Research Scholarship. We thank Mr. Tom Mourey and Ms. Lisa Slater for GPC analysis of poly(1,1,1-trifluoro-2,3-epoxypropane) and Dr. Ivan Keresztes for assistance with the NMR analysis of 3.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleEnantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalysten
dc.typeArticleen
dc.identifier.journalJournal of the American Chemical Societyen
dc.contributor.institutionCornell University, Ithaca, United Statesen
kaust.grant.numberKUS-C1-018-02en
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