Yu Zhenjie, Zou Zhufan, Wang Ran, Li Guangyi, Wang Aiqin, Cong Yu, Zhang Tao, Li Ning
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian, 116023, China.
University of Chinese Academy of Sciences, 19 A Yuquan Road, Shijingshan District, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202300008. doi: 10.1002/anie.202300008. Epub 2023 Feb 14.
Cyclopentadiene (CPD) and methylcyclopentadiene (MCPD) are important intermediates that have been widely used in the production of high-energy-density rocket fuels, polymers and valuable chemicals. Currently, CPD and MCPD are produced from fossil energies at very low yields, which greatly limits their application. As a solution to this problem, we disclose an alternative two-step bio-route to access CPD and MCPD using xylose or extracted hemicellulose as the feedstock. In the first step, cyclopentanone (CPO) was directly produced by the selective hydrogenolysis of xylose or extracted hemicellulose over a commercial Ru/C catalyst in an acid-free toluene/NaCl aqueous solution biphasic system. In the second step, CPO was selectively converted to CPD by a cascade hydrodeoxygenation/dehydrogenation reaction over zinc molybdate catalysts. When methanol was introduced with CPO and hydrogen, MCPD was selectively obtained by a cascade dehydrogenation/aldol condensation/selective hydrodeoxygenation reaction over zinc molybdate catalysts.
环戊二烯（CPD）和甲基环戊二烯（MCPD）是重要的中间体，已广泛用于生产高能量密度火箭燃料、聚合物和有价值的化学品。目前，CPD和MCPD由化石能源生产，产率极低，这极大地限制了它们的应用。作为解决这一问题的方法，我们公开了一种替代的两步生物路线，以木糖或提取的半纤维素为原料来制备CPD和MCPD。第一步，在无酸甲苯/氯化钠水溶液双相体系中，通过商业Ru/C催化剂对木糖或提取的半纤维素进行选择性氢解直接生产环戊酮（CPO）。第二步，通过钼酸锌催化剂上的级联加氢脱氧/脱氢反应将CPO选择性转化为CPD。当甲醇与CPO和氢气一起引入时，通过钼酸锌催化剂上的级联脱氢/羟醛缩合/选择性加氢脱氧反应选择性获得MCPD。
