Rhodium-Complex-Catalyzed Hydroformylation of Olefins with CO sub(2) and Hydrosilane

A rhodium-catalyzed one-pot hydroformylation of olefins with CO sub(2), hydrosilane, and H sub(2) has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of p...

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Bibliographic Details
Published in:Angewandte Chemie 2017-01, Vol.129 (1), p.316-319
Main Authors: Ren, Xinyi, Zheng, Zhiyao, Zhang, Lei, Wang, Zheng, Xia, Chungu, Ding, Kuiling
Format: Article
Language:English
Subjects:
Aldehydes
Carbon dioxide
Carbon monoxide
Catalysis
Olefins
Reduction
Rhodium
Transformations
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Summary:A rhodium-catalyzed one-pot hydroformylation of olefins with CO sub(2), hydrosilane, and H sub(2) has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO sub(2) reduction to CO and a conventional rhodium-catalyzed hydroformylation with CO/H sub(2). The hydrosilylane-mediated reduction of CO sub(2) in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.Original Abstract: Abfallprodukte fuer Hydroformylierungen: Ein Rhodium-Phosphoramidit-Katalysator ermoglicht die Hydroformylierung von Olefinen zu Aldehyden in Gegenwart von CO sub(2), Hydrosilan und H sub(2). Diese Umsetzung verlaeuft wahrscheinlich ueber Polymethylhydrosiloxan(PMHS)-vermittelte CO sub(2)-Reduktion zu CO und eine gewohnliche Rhodium-katalysierte Hydroformylierung mit CO/H sub(2).
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201608628