Oshida Kento, Yuan Kang, Yamazaki Yukari, Tsukimura Rio, Nishio Hidenori, Nomoto Katsutoshi, Miura Hiroki, Shishido Tetsuya, Jin Xiongjie, Nozaki Kyoko
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397, Japan.
Angew Chem Int Ed Engl. 2024 May 13;63(20):e202403092. doi: 10.1002/anie.202403092. Epub 2024 Mar 18.
The hydrogenolysis of oxygenates such as alcohols and ethers is central to the biomass valorization and also a valuable transformation in organic synthesis. However, a mild and efficient catalyst system for the hydrogenolysis of a large variety of alcohols and ethers with various functional groups is still underdeveloped. Here, we report an aluminum metaphosphate-supported Pt nanoparticles (Pt/Al(PO)) for the hydrogenolysis of a wide variety of primary, secondary, and tertiary alkyl and benzylic alcohols, and dialkyl, aryl alkyl, and diaryl ethers, including biomass-derived furanic compounds, under mild conditions (0.1-1 atm of H, as low as 70 °C). Mechanistic studies suggested that H induces formation of the surface Brønsted acid sites via its cleavage by supported Pt nanoparticles. Accordingly, the high efficiency and the wide applicability of the catalyst system are attributed to the activation and cleavage of C-O bonds by the hydrogen-induced Brønsted acid sites with the assistance of Lewis acidic Al sites on the catalyst surface. The high efficiency of the catalyst implies its potential application in energy-efficient biomass valorization or fine chemical synthesis.
醇类和醚类等含氧化合物的氢解反应对于生物质增值至关重要，也是有机合成中的一种重要转化反应。然而，用于温和高效地氢解具有各种官能团的多种醇类和醚类的催化剂体系仍未得到充分发展。在此，我们报道了一种由偏磷酸铝负载的铂纳米颗粒（Pt/Al(PO)），该催化剂能够在温和条件下（氢气压力为0.1 - 1个大气压，温度低至70°C）对多种伯醇、仲醇、叔醇、苄醇以及二烷基醚、芳基烷基醚和二芳基醚进行氢解反应，其中包括生物质衍生的呋喃类化合物。机理研究表明，氢气通过负载的铂纳米颗粒对其进行裂解从而诱导表面布朗斯特酸位点的形成。因此，该催化剂体系的高效性和广泛适用性归因于在催化剂表面路易斯酸性铝位点的协助下，由氢气诱导产生的布朗斯特酸位点对碳 - 氧键的活化和裂解。该催化剂的高效性意味着它在节能生物质增值或精细化学合成方面具有潜在的应用价值。
