Luan Yi, Cai Zonghui, Li Xiujuan, Ramella Daniele, Miao Zongcheng, Wang Wenyu
School of Materials Science and Engineering, University of Science and Technology Beijing 30 Xueyuan Road, Haidian District Beijing 100083 P. R. China
Department of Chemistry, Temple University-Beury Hall 1901, N. 13th Street Philadelphia PA 19122 USA.
RSC Adv. 2019 Mar 7;9(13):7479-7484. doi: 10.1039/c8ra09600g. eCollection 2019 Mar 1.
A concise synthesis of the sulfonic acid-containing MIL-101 MOF catalyst was reported using commercially available materials. A series of characterization of as-synthesized MIL-101-SOH including SEM, XRD, FTIR, BET and TGA was also demonstrated. Using MIL-101-SOH as a catalyst, an efficient Nozaki-Hiyama allenylation reaction was achieved to generate various polyfunctionalized α-allenic alcohols in high yield and good selectivity. Taking advantage of the high acidity of the MIL-101-SOH MOF structure, such transformations were also achieved under mild reaction conditions and short reaction times. Based on our observed evidence during this study, a mechanism was proposed involving a substrate activation/γ-nucleophilic addition reaction sequence. In addition, the MIL-101-SOH catalyst can be recycled ten times during the Nozaki-Hiyama allenylation reaction without compromising the yield and selectivity.
报道了一种使用市售材料对含磺酸的MIL-101金属有机框架催化剂进行的简洁合成方法。还展示了对合成的MIL-101-SOH进行的一系列表征，包括扫描电子显微镜（SEM）、X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、比表面积分析（BET）和热重分析（TGA）。以MIL-101-SOH为催化剂，实现了高效的野崎-平山联烯化反应，以高收率和良好的选择性生成了各种多官能化α-联烯醇。利用MIL-101-SOH金属有机框架结构的高酸度，此类转化反应也能在温和的反应条件和较短的反应时间内实现。基于我们在本研究中观察到的证据，提出了一种涉及底物活化/γ-亲核加成反应序列的机理。此外，MIL-101-SOH催化剂在野崎-平山联烯化反应中可循环使用十次，而不会影响收率和选择性。
