Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

Renee M. Thomas; Peter C. B. Widger; Syud M. Ahmed; Ryan C. Jeske; Wataru Hirahata; Emil B. Lobkovsky; Geoffrey W. Coates

doi:10.1021/ja1058422

Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

Renee M. Thomas, Peter C. B. Widger, Syud M. Ahmed, Ryan C. Jeske, Wataru Hirahata, Emil B. Lobkovsky, Geoffrey W. Coates

Research output: Contribution to journal › Article › peer-review

137 Scopus citations

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.

Original language	English (US)
Pages (from-to)	16520-16525
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	132
Issue number	46
DOIs	https://doi.org/10.1021/ja1058422
State	Published - Nov 24 2010
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-C1-018-02
Acknowledgements: 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.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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10.1021/ja1058422

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title = "Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst",

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. {\textcopyright} 2010 American Chemical Society.",

author = "Thomas, {Renee M.} and Widger, {Peter C. B.} and Ahmed, {Syud M.} and Jeske, {Ryan C.} and Wataru Hirahata and Lobkovsky, {Emil B.} and Coates, {Geoffrey W.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-018-02 Acknowledgements: 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. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

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N2 - 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.

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Enantioselective Epoxide Polymerization Using a Bimetallic Cobalt Catalyst

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