Manganese-catalyzed hydroboration of carbon dioxide and other challenging carbonyl groups

Reductive functionalization of the C=O unit in carboxylic acids, carbonic acid derivatives, and ultimately in carbon dioxide itself is a challenging task of key importance for the synthesis of value-added chemicals. In particular, it can open novel pathways for the valorization of non-fossil feedsto...

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Bibliographic Details
Published in:Nature communications 2018-10, Vol.9 (1), p.4521-9, Article 4521
Main Authors: Erken, Christina, Kaithal, Akash, Sen, Suman, Weyhermüller, Thomas, Hölscher, Markus, Werlé, Christophe, Leitner, Walter
Format: Article
Language:English
Subjects:
140/131
140/58
639/638/224/685
639/638/77/888
Carbon dioxide
Carbon monoxide
Carbonates
Carbonic acid
Carbonyl groups
Carbonyls
Carboxylic acids
Catalysis
Catalysts
Coordination compounds
Crystallography
Heavy metals
Humanities and Social Sciences
Hydroboration
Manganese
Metals
multidisciplinary
Organic chemistry
Raw materials
Reducing agents
Science
Science (multidisciplinary)
Substrates
Sustainable development
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Summary:Reductive functionalization of the C=O unit in carboxylic acids, carbonic acid derivatives, and ultimately in carbon dioxide itself is a challenging task of key importance for the synthesis of value-added chemicals. In particular, it can open novel pathways for the valorization of non-fossil feedstocks. Catalysts based on earth-abundant, cheap, and benign metals would greatly contribute to the development of sustainable synthetic processes derived from this concept. Herein, a manganese pincer complex [Mn(Ph 2 PCH 2 SiMe 2 ) 2 NH(CO) 2 Br] ( 1 ) is reported to enable the reduction of a broad range of carboxylic acids, carbonates, and even CO 2 using pinacolborane as reducing agent. The complex is shown to operate under mild reaction conditions (80–120 °C), low catalyst loadings (0.1–0.2 mol%) and runs under solvent-less conditions. Mechanistic studies including crystallographic characterisation of a borane adduct of the pincer complex ( 1 ) imply that metal-ligand cooperation facilitates substrate activation. Catalytic reduction of CO 2 and biomass derivatives is of great current interest from a sustainable chemistry perspective. Here, the authors report a manganese pincer complex able to reduce under mild conditions carboxylic acids, carbonates and even carbon dioxide using pinacolborane as reducing agent.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-018-06831-9