N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide)

Stefan Naumann; Anthony W Thomas; Andrew P Dove

doi:10.1002/anie.201504175

N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide)

Stefan Naumann
, Anthony W Thomas
, Andrew P Dove

Chemistry

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

70 Citations (Scopus)

121 Downloads (Pure)

Abstract

The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (Đ(M)<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.

Original language	English
Pages (from-to)	9550-9554
Number of pages	5
Journal	Angewandte Chemie (International Edition)
Volume	54
Issue number	33
Early online date	1 Jul 2015
DOIs	https://doi.org/10.1002/anie.201504175
Publication status	Published - 10 Aug 2015

Bibliographical note

© 2015 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

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Naumann_et_al_N-Heterocyclic_olefins_as_organocatalysts_Angewandte_Chemie_International_Edition_2015
Naumann, S., Thomas, A.W. and Dove, A.P. (2015), N‐Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well‐Defined Poly(propylene oxide). Angew. Chem. Int. Ed., 54: 9550-9554. doi:10.1002/anie.201504175
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https://doi.org/10.1002/anie.201504175Licence: Creative Commons: Attribution (CC BY)

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title = "N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide)",

abstract = "The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity ({\D}(M)<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.",

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note = "{\textcopyright} 2015 The Authors. Published by Wiley‐VCH Verlag GmbH \& Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.",

year = "2015",

month = aug,

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doi = "10.1002/anie.201504175",

language = "English",

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T1 - N-Heterocyclic Olefins as Organocatalysts for Polymerization

T2 - Preparation of Well-Defined Poly(propylene oxide)

AU - Naumann, Stefan

AU - Thomas, Anthony W

AU - Dove, Andrew P

N1 - © 2015 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

PY - 2015/8/10

Y1 - 2015/8/10

N2 - The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (Đ(M)<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.

AB - The metal-free polymerization of propylene oxide (PO) using a special class of alkene—N-heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal-free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (Đ(M)<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.

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DO - 10.1002/anie.201504175

M3 - Article

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JO - Angewandte Chemie (International Edition)

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IS - 33

ER -

N-Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well-Defined Poly(propylene oxide)

Abstract

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