Abstract
A new catalytic route has been developed for the coupling of epoxides and CO2 affording polymerizable six-membered bicyclic carbonates. Cyclic epoxides equipped with a β-positioned OH group can be transformed into structurally diverse bicyclic cyclic carbonates in good yields and with high selectivity. Key to the chemo-selectivity is the difference between the reactivity of syn- and anti-configured epoxy alcohols, with the latter leading to six-membered ring carbonate formation in the presence of a binary AlIII aminotriphenolate complex/DIPEA catalyst. X-ray analyses show that the conversion of the syn-configured substrate evolves via a standard double inversion pathway providing a five-membered carbonate product, whereas the anti-isomer allows for activation of the oxirane unit of the substrate opposite to the pendent alcohol. The potential use of these bicyclic products is shown in ring-opening polymerization offering access to rigid polycarbonates with improved thermal resistance.
Original language | English |
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Article number | e202205053 |
Number of pages | 6 |
Journal | Angewandte Chemie - International Edition |
Volume | 61 |
Issue number | 27 |
Early online date | 20 Apr 2022 |
DOIs | |
Publication status | Published - 4 Jul 2022 |
Bibliographical note
Funding Information:We thank the Cerca program/Generalitat de Catalunya, ICREA, MINECO (PID2020-112684GB-100) and the Ministerio de Ciencia e Innovación (Severo Ochoa Excellence Accreditation 2020–2023 CEX2019-000925-S) for support. C.Q. and W.S. acknowledge the Chinese Research Council for predoctoral fellowships (2018-06200078 and 2021-06350046).
Publisher Copyright:
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Keywords
- Carbon Dioxide
- Cyclic Carbonates
- Homogeneous Catalysis
- Monomers
- Ring-Opening Polymerization
ASJC Scopus subject areas
- Catalysis
- General Chemistry