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http://hdl.handle.net/10773/26614
Title: | Efficient isomerization of α-pinene oxide to campholenic aldehyde promoted by a mixed-ring analogue of molybdenocene |
Author: | Bruno, Sofia M. Valente, Anabela A. Pillinger, Martyn Amelse, Jeffrey Romão, Carlos C. Gonçalves, Isabel S. |
Keywords: | Renewable resources Terpenes Rearrangement Homogeneous catalysis Molybdenum Metallocenes Lewis acids Ionic liquids |
Issue Date: | 19-Aug-2019 |
Publisher: | American Chemical Society |
Abstract: | The MoIV complex [(eta5-indenyl)(eta5-cyclopentadienyl)Mo(MeCN)2](BF4)2 (1) has been used to promote two acid-catalyzed epoxide ring-opening reactions under ambient conditions. The alcoholysis of styrene oxide in neat ethanol gave 2-ethoxy-2-phenylethanol in quantitative yield within 10 min. The use of an ionic liquid (IL) as cosolvent benefitted catalyst solubility and recycling while not impairing catalytic performance. Complex 1 in 1,2-dichloroethane was effective for the isomerization of alpha-pinene oxide to campholenic aldehyde (CPA), leading to 87% yield at 1 h reaction. The same yield could be achieved within 1 min by using the IL [Choline][NTf2] as solvent. CPA yields at 1 min reached near-quantitative values (98%) upon recycling of the catalyst/IL mixture, demonstrating an unparalleled combination of activity, selectivity and recyclability for this commercially important reaction. Considering the catalytic features of the 1/IL system, a CPA process flow diagram is proposed and compared to patented technology. |
Peer review: | yes |
URI: | http://hdl.handle.net/10773/26614 |
DOI: | 10.1021/acssuschemeng.9b03087 |
ISSN: | 2168-0485 |
Publisher Version: | https://pubs.acs.org/doi/10.1021/acssuschemeng.9b03087 |
Appears in Collections: | CICECO - Artigos |
Files in This Item:
File | Description | Size | Format | |
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Post-print_acssuschemeng.9b03087.pdf | 1.33 MB | Adobe PDF | View/Open |
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