文献类型：期刊文献

英文题名：A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O-H bond insertion

作者：Zhao, Jie[1,2];Ji, Shufang[3];Guo, Chenxi[4];Li, Haijing[5];Dong, Juncai[5];Guo, Ping[1,2];Wang, Dingsheng[3];Li, Yadong[3];Toste, F. Dean[6,7]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Mat & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Mat & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, Shanghai, Peoples R China;[3]Tsinghua Univ, Dept Chem, Beijing, Peoples R China;[4]Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian, Peoples R China;[5]Chinese Acad Sci, Inst High Energy Phys, Beijing Synchrotron Radiat Facil, Beijing, Peoples R China;[6]Lawrence Berkeley Natl Lab, Chem Sci Div, Berkeley, CA 94720 USA;[7]Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

年份：2021

卷号：4

期号：6

起止页码：523

外文期刊名：NATURE CATALYSIS

收录：;EI(收录号：20212510545155);WOS:【SCI-EXPANDED(收录号:WOS:000664141000008)】；

基金：J.Z. acknowledges support from the Shanghai Municipal Science and Technology Major Project (2018SHZDZX03) and the Program of Introducing Talents of Discipline to Universities (B16017). S.J., D.W. and Y L. acknowledge the National Key R&D Program of China (2018YFA0702003) and the National Natural Science Foundation of China (21890383). They thank the BL14W1 station in Shanghai Synchrotron Radiation Facility (SSRF). J.D. acknowledges the Youth Innovation Promotion Association of Chinese Academy of Sciences (2018017). F.D.T. acknowledges support by the Director, Office of Science, Office of Basic Energy Science and the Division of Chemical Sciences, Geosciences, and Bioscience of the US Department of Energy at Lawrence Berkeley National Laboratory (grant DE-AC0205CH1123). We thank B. Ye from ShanghaiTech University for helpful discussions.

语种：英文

外文关键词：Organic compounds - Density functional theory - Iridium - Atoms - Catalyst selectivity

摘要：Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C-O bonds. Achieving site-selective functionalization of alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report a strategy for selective carbenoid O-H insertion that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities for organic transformations by merging material science and catalysis. This catalytic protocol delivers excellent selectivities (up to 99:1) for the functionalization of aliphatic over phenolic O-H bonds, whereas the analogous homogeneous catalyst, Ir(ttp)COCI (ttp = 5,11),15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest that the site-selectivity derives from the lower oxidation state of the iridium metal centre in the heterogeneous catalyst and its impact on the absorption energies of the reactants. These results showcase an example of a heterogeneous single-atom catalyst providing superior site-selectivity and provide a complementary strategy to address challenges in catalysis for organic synthesis.