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(Ph2PCH2SiMe2)2NH(CO)2Br] (1) is reported to enable the reduction of a broad range of carboxylic acids, carbonates, and even CO2 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.
Highlights
Reductive functionalization of the C=O unit in carboxylic acids, carbonic acid derivatives, and in carbon dioxide itself is a challenging task of key importance for the synthesis of value-added chemicals
The catalytic reduction of the C=O unit in carboxylic acids (RCO2H), carbonic acid derivatives (O=C(OR)2), and carbon dioxide (CO2) itself is of great current interest for the development of sustainable chemical value chains
We report a Mn pincer complex that enables catalytic reductive functionalization for a wide range of structurally divers substrates through hydroboration of free carboxylic acids, cyclic five- and six-membered carbonates, linear carbonates, and even carbon dioxide
Summary
Reductive functionalization of the C=O unit in carboxylic acids, carbonic acid derivatives, and in carbon dioxide itself is a challenging task of key importance for the synthesis of value-added chemicals. We report a Mn pincer complex that enables catalytic reductive functionalization for a wide range of structurally divers substrates through hydroboration of free carboxylic acids, cyclic five- and six-membered carbonates, linear carbonates, and even carbon dioxide.
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