Manganese-catalyzed hydroboration of carbon dioxide and other challenging carbonyl groups.
basic_science · Level V
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- Record sourced from PubMed, PMID 30375381.
- Also identified by DOI 10.1038/s41467-018-06831-9 and PMC identifier 6207666.
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Abstract
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<sub>2</sub>PCH<sub>2</sub>SiMe<sub>2</sub>)<sub>2</sub>NH(CO)<sub>2</sub>Br] (1) is reported to enable the reduction of a broad range of carboxylic acids, carbonates, and even CO<sub>2</sub> 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.