碳化铁催化氢气气氛下苯甲醇脱氧偶联制备联苄类化学品

doi:10.1016/S1872-2067(24)60256-1

催化学报 ›› 2025, Vol. 71: 179-186.DOI: 10.1016/S1872-2067(24)60256-1

碳化铁催化氢气气氛下苯甲醇脱氧偶联制备联苄类化学品

王一潮^a^,^b, 张磊磊^a^,^*(), 潘晓丽^a, 王爱琴^a^,^*(), 张涛^a

^a中国科学院大连化学物理研究所, 中国科学院应用催化科学技术重点实验室, 辽宁大连 116023
^b中国科学院大学, 北京 100049

收稿日期:2024-12-26 接受日期:2025-01-20 出版日期:2025-04-18 发布日期:2025-04-13
通讯作者: * 电子信箱: zhangleilei@dicp.ac.cn (张磊磊), aqwang@dicp.ac.cn (王爱琴).
基金资助:
国家重点研发计划(2023YFA1506603);国家自然科学基金(22132006);国家自然科学基金(22172159);中国科学院稳定支持基础研究领域青年团队计划(YSBR-022);中国科学院青年创新促进会(2022185)

Iron carbide-catalyzed deoxygenative coupling of benzyl alcohols toward bibenzyls under hydrogen atmosphere

Yichao Wang^a^,^b, Leilei Zhang^a^,^*(), Xiaoli Pan^a, Aiqin Wang^a^,^*(), Tao Zhang^a

^aCAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-12-26 Accepted:2025-01-20 Online:2025-04-18 Published:2025-04-13
Contact: * E-mail: zhangleilei@dicp.ac.cn (L. Zhang), aqwang@dicp.ac.cn (A. Wang).
Supported by:
National Key R&D Program of China(2023YFA1506603);National Natural Science Foundation of China(22132006);National Natural Science Foundation of China(22172159);CAS Project for Young Scientists in Basic Research(YSBR-022);Youth Innovation Promotion Association CAS(2022185)

摘要/Abstract

摘要：

过渡金属催化的碳-碳成键反应是现代化学合成的基石. 经典的碳-碳偶联反应, 如钯催化的交叉偶联反应, 往往使用卤代烃作为亲电试剂. 近年来, 考虑到醇类化合物在价格和无卤化废弃物生成等方面的优势, 醇参与的碳-碳偶联反应得到了广泛关注. 然而, 醇的C(sp³)−O的解离能(BDEs)很高, 键极性较卤代烃更低, 导致了醇的直接活化转化存在相当大的挑战性. 醇参与的偶联反应模式包括交叉偶联和同偶联, 其中, 醇的还原脱氧同偶联反应在一次反应中需要脱除两个羟基, 同时形成一根新的碳−碳键, 在催化体系的设计方面存在很大挑战性. 苄醇的脱氧同偶联反应得到的联苄类化学品在药物、化学工程和聚合物领域有潜在的应用价值. 经典的联苄类化学品的催化合成路线包括卤代苄的脱卤二聚、苄基格式试剂的偶联及1, 2-二氯乙烷和苯的傅克反应等, 这些体系往往会导致卤代废弃物的生成. 目前, 从苯甲醇类化合物出发制备联苄化学品的工作主要集中于均相体系, 如铼、钼和钌等配合物催化剂配合三苯基膦, 水合肼等强还原剂, 但这些体系在催化剂的分离回收和强还原剂的价格和安全性方面均存在问题. 考虑到醇羟基(-OH)在催化循环设计中的理想去向是与氢(-H)结合生成水, 本文的目标是开发一种能够介导苯甲醇在氢气气氛下还原脱氧偶联制备联苄化学品的非均相催化体系.
目前文献中关于苯甲醇脱氧偶联制联苄的非均相体系报道极少, 该反应催化剂设计的关键在于在构造具有适度亲氧性的金属中心, 在形成强金属−氧键促进醇碳−氧键活化的同时, 要保证催化剂在氢气气氛中能够还原恢复初始状态. 受到费托合成反应的启发, 本文将碳化铁催化剂用于苯甲醇类化合物的脱氧偶联反应. 首先, 通过还原-碳化法合成了一系列碳化铁基催化剂, 考察了不同金属助剂对苯甲醇转化率和目标产物联苄选择性的影响. 研究发现, 铱促进的碳化铁催化剂性能最佳, 在220 °C和0.60 MPa氢气的反应条件下, 最优的Ir_0.1/Fe⁰@Fe₅C₂催化剂展现出了100%的苯甲醇转化率和60.3%的偶联产物收率(56.4%联苄+3.9%三聚产物). 一锅条件下, 该催化剂在12 h内的联苄产量为5.4 g_bibenzyl/g_cat., 是金属铁催化剂的十倍. 随后, 对反应的底物适用范围进行了考察. 二级苄醇和含给电子取代基(如醚键)的一级苄醇均能得到良好的联苄产物收率, 最高的分离收率为85%. 当向反应体系中引入烯烃后, 发现苯甲醇和烯烃倾向于发生三分子偶联反应, 形成更复杂的骨架结构. 该反应适用于取代苯乙烯和1, 2-二苯乙烯类底物, 收率适中. 后续的克级规模放大证明了以上两种反应模式的实用性. 最后, 通过X-射线衍射、透射电镜、X-射线光电子能谱和⁵⁷Fe穆斯堡尔谱等手段揭示了催化剂结构. Ir_0.1/Fe⁰@Fe₅C₂催化剂是外围碳化铁包裹内部未渗碳金属铁的核壳结构, 金属铱以纳米粒子形式分散在催化剂表面. 进一步的自由基捕获实验证明了反应经由苄基自由基历程, 苯甲醇碳−氧键在反应中发生均裂. 红外实验和控制实验进一步阐释了反应机理: 苯甲醇的氧−氢键在催化剂表面裂解, 形成表面醇氧物种和吸附氢物种, 随后碳−氧键在高温条件下均裂形成苄基自由基和表面吸附氧, 最后在氢气气氛中催化剂恢复初始状态. 反应中金属铱可能促进了碳自由基物种的偶联及催化剂上氧物种的还原.
综上, 本文首次证明了碳化铁催化剂能够高效催化苯甲醇还原偶联制备联苄类化学品. 该方法避免了含卤试剂的使用, 副产物为水, 底物适用性较好. 该体系为后续醇参与的直接碳−氧键活化反应催化剂的开发提供了有益借鉴.

关键词: 脱氧偶联反应, 苯甲醇, 联苄, 碳化铁, 氢气气氛

Abstract:

The direct deoxygenative homo-coupling of benzyl alcohols holds great promise to build up bibenzyl motifs in organic synthesis, yet it remains a grand challenge in selectivity and activity control. Herein, we first discovered that iron carbide catalysts displayed high efficiency and selectivity in the catalytic deoxygenative homo-coupling of benzyl alcohols into bibenzyls using H₂ as the reductant. Ir-promoted Fe⁰@Fe₅C₂ gave the best performance among the investigated catalysts, and a broad scope of substrates with diverse functional groups could be smoothly converted into bibenzyls, with the yield up to 85%. In addition, in the presence of alkenes, three-component coupling reactions between alcohols and alkenes were also for the first time achieved to construct more complex multi-ring molecules. The radical-trapping experiment and FTIR measurements revealed the radical nature of the reaction and the significantly promoted C-O bond activation after carbonization, respectively. This work will provide guidelines for the rational design of efficient and selective catalysts for the alcohol-involved carbon-carbon coupling reactions.

Key words: Deoxygenative coupling reaction, Benzyl alcohols, Bibenzyls, Iron carbide, Hydrogen atmosphere

王一潮, 张磊磊, 潘晓丽, 王爱琴, 张涛. 碳化铁催化氢气气氛下苯甲醇脱氧偶联制备联苄类化学品[J]. 催化学报, 2025, 71: 179-186.

Yichao Wang, Leilei Zhang, Xiaoli Pan, Aiqin Wang, Tao Zhang. Iron carbide-catalyzed deoxygenative coupling of benzyl alcohols toward bibenzyls under hydrogen atmosphere[J]. Chinese Journal of Catalysis, 2025, 71: 179-186.

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图/表 8

Scheme 1. Applications (a), typical synthetic methods of bibenzyl (b), and the methodology developed in this work (c).

Fig. 1. Catalyst screening for the deoxygenative coupling of benzyl alcohol toward bibenzyl. Reaction conditions: 2.5 mmol benzyl alcohol, 120 mg catalyst (mass based on Fe2O3), 8 mL n-hexane, 0.6 MPa H2, 220 °C, 12 h, 500 r min-1, dodecane was added as internal standard. ^Trimer: 1,2,3- triphenylpropane. *The carbonization time was lengthened to 8 h. &240 mg Fe2O3.

Scheme 2. The substrate replacement experiments. Reaction conditions: 2.5 mmol benzyl alcohol, 120 mg catalyst (mass based on Ir0.1/Fe2O3), 8 mL n-hexane, 0.6 MPa gas, 220 °C, 12 h, 500 r min-1.

Scheme 3. The substrate scope of deoxygenative coupling of various benzyl alcohols catalyzed by Ir0.1/Fe0@Fe5C2. Reaction conditions: 2 mmol benzyl alcohol, 120 mg catalyst (mass based on Ir0.1/Fe2O3), 8 mL THF, 0.5 MPa H2, 220 °C, 12 h, 400 r min-1, dodecane was added as internal standard. Isolated yields were given. *GC yields.

Scheme 4. Three-component coupling reactions between benzyl alcohols and alkenes. Reaction conditions: 4 mmol benzyl alcohol, 1 mmol alkene, 120 mg Ir0.1/Fe0@Fe5C2, 8 mL n-hexane, 0.4 MPa H2, 220 °C, 12 h, 400 r min-1. Isolated yields were given. *GC yields.

Fig. 2. (a) XRD patterns in different stages during the preparation process of the Ir0.1/Fe0@Fe5C2 catalyst. (b) The AC-HAADF-STEM image of Ir0.1/Fe0@Fe5C2. In situ 57Fe M?ssbauer spectra of Ir0.1/Fe0@Fe5C2 (c) and Fe0@Fe5C2 (d) catalysts and the corresponding fitting results (e). (f) Fe 3d XPS spectra of Fe0@Fe5C2 and Ir0.1/Fe0@Fe5C2 [22] catalysts.

Fig. 3. (a) Radical-trapping experiment. (b) FTIR spectra of benzyl alcohol adsorption on different iron catalysts.

Fig. 4. The proposed reaction mechanism.

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碳化铁催化氢气气氛下苯甲醇脱氧偶联制备联苄类化学品

Iron carbide-catalyzed deoxygenative coupling of benzyl alcohols toward bibenzyls under hydrogen atmosphere

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