Hou, Zhaomin - RIkagaku KENkyusho/Institute of Physical and Chemical Research - RIKEN Center for Sustainable Resource Science and Organometallic Chemistry Laboratory

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Hou, Zhaomin Professor 收藏完善纠错
RIkagaku KENkyusho/Institute of Physical and Chemical Research RIKEN Center for Sustainable Resource Science and Organometallic Chemistry Laboratory
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个人简介

Education and professional positions 1982 B.Sc. China University of Petroleum 1986 M.Sc. Kyushu University 1989年 Postdoctoral Researcher, RIKEN 1990年 Special Postdoctoral Researcher, RIKEN 1991年 Postdoctoral Researcher, University of Windsor, Canada (Prof. Douglas Stephan) 1993 Research Scientist, RIKEN 1997 Senior Scientist, RIKEN 2002-present Chief Scientist, Director of Organometallic Chemistry Laboratory, RIKEN 2013-present Group Director, Advanced Catalysis Research Group Deputy Center Director, RIKEN Center for Sustainable Resource Science Concurrent appointments 2003-present Visiting Professor, Graduate School of Science and Engineering, Saitama University 2008-present Visiting Professor, Tokyo Institute of Technology Awards and Honors 1996 Japan Society of Coordination Chemistry Award for Young Scientists 1997 Rare Earth Society of Japan Award for Young Scientists 2000 Progress Award in Synthetic Organic Chemistry, Japan 2007 JSPS Prize 2007 Mitsui Chemicals Catalysis Science Award 2007 The Chemical Society of Japan Award for Creative Work 2008 The Commendation for Science and Technology by the Minister of Education, Culture,Sports, Science and Technology: the Prizes for Science and Technology in Research Category 2009 The Rare Earth Society of Japan Award 2011 Asian Core Program Lectureship Award 2012 The Award of the Society of Polymer Science, Japan 2012 Asian Core Program Lectureship Award 2013 Pioneers from Asia, The 15th Asian Chemical Congress 2014 Chinese Chemical Society Yaozeng Huang Award in Organometallic Chemistry 2014 Seventh Negishi-Brown Lectures, Purdue University 2016 Nagoya Silver Medal 2018 Swiss Chemical Society (SCS) Lectureships 2018 Asian CORE Program/Advanced Research Network 2019 Lectureship Award Chemical Society of Japan Awards 2020 RIKEN EIHO Award (RIKEN Significant Achievement Award) 2022 Japan Academy Prize 2023 The Chemistry Society of Japan Award for Honorary Membership

研究领域

1.Rare Earth Catalysts for Regio- and Stereospecific Polymerization Unlike the majority of transition metals which display multiple oxidation states, rare-earth metals typically exist in the 3+ oxidation state under normal conditions. This “redox-inactive” feature makes rare-earth metals unique candidates for the formation of true “single-site” polymerization catalysts. With an aim to create novel high-performance polymeric materials, our research program in part focuses on the development of highly active and selective polymerization catalysts based on cationic rare-earth metal monoalkyl complexes. Utilizing the singular character of these catalytic systems, we have achieved various novel polymerization and copolymerization reactions. These have led to the formation of a new family of polymeric materials showing unique chemical, physical and mechanical properties. 2.Rare-Earth Catalysts for Efficient Organic Synthesis We have found that the aforementioned cationic rare-earth alkyl species can also serve as unique catalysts for a number of important chemical transformations in organic synthesis. These include the regio- and stereoselective methylalumination of alkynes and alkenes, the hydroarylation of alkenes, styrenes and allenes, and the enantioselective C-H alkylation of pyridines with simple alkenes. 3.Utilization of CO2　as a C1-Building Block for Fine Chemical Synthesis Carbon dioxide (CO2) is a naturally abundant, readily available, non-toxic, and inherently renewable carbon resource. Accordingly, the use of CO2 as a chemical feedstock for preparing value-added chemicals currently attracts much interest from synthetic organic chemists as well as chemical industry. We have recently found that N-heterocyclic carbene copper (NHC-Cu) complexes can serve as excellent catalysts for the carboxylation of various organic substrates with CO2. This catalyst system features broad substrate scope, high regio- and stereoselectivity, excellent functional group tolerance, and occurs via a well-defined reaction mechanism. 4.Activation of Inactive Molecules by Molecular Metal Hydride Clusters The cooperation of multiple metal centers can facilitate the activation of unreactive molecules which is difficult to achieve by just a single metal site. Metal hydrides are among the most reactive organometallic compounds and are fundamental components in a wide range of stoichiometric and catalytic reactions. The investigation of the reactivity of multi-metallic hydride complexes with inactive molecules is therefore of much interest and importance. We have recently found that multi-metallic rare-earth and group 4 metal hydride complexes can show unique synergistic effects on the activation of small molecules such as CO, CO2, H2 and N2 as well as on the activation of the carbon skeleton of aromatic compounds such as benzene and toluene.

近期论文

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Q. Zhuo, J. Yang, X. Zhou, T. Shima, Y. Luo, Z. Hou,“Dinitrogen Cleavage and Multicoupling with Isocyanides in a Dititanium Dihydride Framework”J. Am. Chem. Soc.,2024.DOI:10.1021/jacs.4c02905 X. Cong, N. Hao, A. Mishra, Q. Zhuo, K. An, M. Nishiura, Z. Hou,“Regio- and Diastereoselective Annulation of α,β-Unsaturated Aldimines with Alkenes via Allylic C(sp3)–H Activation by Rare-Earth Catalysts”J. Am. Chem. Soc.,2024.DOI:10.1021/jacs.4c02144 S. Kamiguchi, K. Asakura, T. Shibayama, T. Yokaichiya, T. Ikeda, A. Nakayama, K. Shimizu, and Z. Hou,"Catalytic ammonia synthesis on HY-zeolite-supported angstrom-size molybdenum cluster",Chem. Sci., 2024,15, 2914-2922　DOI:10.1039/D3SC05447K L. Huang, Y. Yang, J. Shao, G. Xiong, H. Wang, M. Nishiura, and Z. Hou,"Synthesis of Tough and Fluorescent Self-Healing Elastomers by Scandium-Catalyzed Terpolymerization of Pyrenylethenylstyrene, Ethylene, and Anisylpropylene",J. Am. Chem. Soc.,2024.　DOI:10.1021/jacs.3c12342 X. Cong, Q. Zhuo, N. Hao, A. Mishra, M. Nishiura, Z. Hou,"Divergent Synthesis of Multi-Substituted Aminotetralins via [4+2] Annulation of Aldimines with Alkenes by Rare-Earth-Catalyzed Benzylic C(sp3)−H Activation",Angew. Chem. Int. Ed., 2024.　10.1002/anie.202318203 Q. Zhuo, J. Yang, X. Zhou, T. Shima, Y. Luo, and Z. Hou,"Aza-Michael Addition of Dinitrogen to α,β-Unsaturated Carbonyl Compounds in a Dititanium Framework",J. Am. Chem. Soc., 2023.　DOI:10.1021/jacs.3c08715 M. Takimoto, Z. Hou,"Regioselective Carbozincation and Further Functionalization of Allenamides Catalyzed by an N–Heterocyclic Carbene (NHC)–Copper Complex",Asian. J. Org. Chem., 2023, e202300372. A.Mishra, X. Cong, M. Nishiura, and Z. Hou,"Enantioselective Synthesis of 1-Aminoindanes via [3 + 2] Annulation of Aldimines with Alkenes by Scandium-Catalyzed C–H Activation",J. Am. Chem. Soc., 2023. https://doi.org/10.1021/jacs.3c06482　 X. Lin, K. An, Q. Zhuo, M. Nishiura, X. Cong, Z. Hou,"Diastereo- and Enantioselective Hydrophosphination of Cyclopropenes under Lanthanocene Catalysis",Angew. Chem. Int. Ed., 2023. https://doi.org/10.1002/anie.202308488　 Y. So, C. To, M. Guru, T. Shima, and Z. Hou,"Hydrodeoxygenative Coupling and Transformation of Aldehydes at a N2-Derived Tetranuclear Titanium Imide/Hydride Framework",J. Am. Chem. Soc., 2023, 145, 16906-16912.　DOI: 10.1021/jacs.3c05525　 Y. Wang, L. Huang, Z. Hou and F. Guo,"Polymerization of α-olefins and their copolymerization with ethylene by half-sandwich scandium catalysts with an N-heterocyclic carbene ligand",Polym. Chem., 2023, 14, 828–838. 　DOI: 10.1039/d2py01526a　 X. Cong, L. Huang, Z. Hou,"C–H functionalization with alkenes, allenes, and alkynes by half-sandwich rare-earth catalysts",Tetrahedron, 2023, 135, 133323.　https://doi.org/10.1016/j.tet.2023.133323　 - Q. Zhuo, X. Zhou, T. Shima, Z. Hou,"Dinitrogen Activation and Addition to Unsaturated C‒E (E = C, N, O, S) Bonds Mediated by Transition Metal Complexes",Angew. Chem. Int. Ed., 2023, 62, e202218606. DOI: 10.1002/anie.202218606 H. Sahoo, L. Zhang, J. Cheng, M. Nishiura, and Z. Hou,"Auto-Tandem Copper-Catalyzed Carboxylation of Undirected Alkenyl C–H Bonds with CO2 by Harnessing β-Hydride Elimination",J. Am. Chem. Soc., 2022, 144, 23585-23594.　 DOI: 10.1021/jacs.2c10754　 M. Takimoto, M. Liu, M. Nishiura, and Z. Hou,"Regioselective Benzylic C−H Alumination and Further Functionalization of 2‑Alkylpyridines by Yttrium Catalyst",ACS Catal., 2022, 12, 13792-13804.　 DOI: 10.1021/acscatal.2c04396　 A. Mishra, P. Wu, X. Cong, M. Nishiura, G. Luo, and Z. Hou,"Exo-Selective Intramolecular C−H Alkylation with 1,1-Disubstituted Alkenes by Rare-Earth Catalysts: Construction of Indanes and Tetralins with an All-Carbon Quaternary Center",ACS Catal., 2022, 12, 12973–12983.　 DOI: 10.1021/acscatal.2c03681　 W. Xu, X. Cong, K. An, S. Lou, Z. Li, M. Nishiura, T. Murahashi, and Z. Hou,"Regio- and Diastereoselective Formal [2+2] Cycloaddition of Allenes with Amino-Functionalized Alkenes by Rare-Earth-Catalyzed C(sp2)–H Activation",Angew. Chem. Int. Ed., 2022, 61, e202210624.DOI: 10.1002/anie.202210624　 H. Wang, Y. Yang, M. Nishiura, Y. Hong, Y. Nishiyama, Y. Higaki, Z. Hou,"Making Polyisoprene Self-Healable through Microstructure Regulation by Rare-Earth Catalysts",Angew. Chem. Int. Ed., 2022, 61, e202210023.DOI: 10.1002/anie.202210023 L. Jiang, Y. Wang, H. Sun, T. Fu, Z. Hou, F. Guo,"Phosphine-Functionalized Syndiotactic Polystyrenes: Synthesis and Application to Immobilization of Transition Metal Nanoparticle Catalysts", Chem.Eur. J., 2022, 28, e202202113.　 https://doi.org/10.1002/chem.202202113 F. You, X. Kang, M. Nishiura, J. Zhai, S. Xu, J. Wang, X. Shi, and Z. Hou,"Living 3,4-Isoselective (Co)polymerization of Biobased β-Farnesene Catalyzed by Phosphine-Functionalized Fluorenyl Rare-Earth Metal Catalysts",Macromolecules, 2022, 55, 5049–5057.　 https://doi.org/10.1021/acs.macromol.2c00887　 T. Fu, L. Jiang, H. Sun, Z. Hou and F. Guo,"Scandium-catalyzed stereoselective block and alternating copolymerization of diphenylphosphinostyrenes and isoprene", Polym. Chem., 2022, 13, 3498-3505.　DOI: 10.1039/d2py00290f　 W. Zhou, X. Cong, M. Nishiura, and Z. Hou,"Synthesis of allylanilines via scandium-catalysed benzylic C(sp3)–H alkenylation with alkynes", Chem. Commun., 2022, 58, 7257–7260.　 DOI: 10.1039/d2cc02489f　 Q. Zhuo, J. Yang, Z. Mo, X. Zhou, T. Shima, Y. Luo, and Z. Hou, "Dinitrogen Cleavage and Functionalization with Carbon Dioxide in a Dititanium Dihydride Framework", J. Am. Chem. Soc., 2022. DOI: 10.1021/jacs.2c01851 J. Yang, Q. Zhuo, Z. Mo, Z. Hou and Y. Luo,"Theoretical mechanistic insights into dinitrogen cleavage by a dititanium hydride complex bearing PNP-pincer ligands",Dalton Trans., 2022, DOI: 10.1039/D1DT03852D X. Cong, Q. Zhuo, N. Hao, Z. Mo, G. Zhan, M. Nishiura, Z. Hou, "Regio- and Diastereoselective [3 + 2] Annulation of Aliphatic Aldimines with Alkenes by Scandium-Catalyzed β-C(sp3)−H Activation",Angew. Chem. Int. Ed., 2021, DOI: 10.1002/anie.202115996 G. Xiong, O. Tardif, M. Nishiura, B. Guan, Z. Hou, "Synthesis and Structure Diversity of Half-Sandwich Rare Earth Dialkynyl Complexes", Helv. Chim. Acta, 2021, DOI: 10.1002/hlca.202100197 S. Lou, G. Luo, S. Yamaguchi, K. An, M. Nishiura, and Z. Hou, "Modular Access to Spiro-dihydroquinolines via Scandium-Catalyzed Dearomative Annulation of Quinolines with Alkynes", J. Am. Chem. Soc., 2021, DOI: 10.1021/jacs.1c10743 Y. Yang, H. Wang, L. Huang, M. Nishiura, Y. Higaki, Z. Hou, "Terpolymerization of Ethylene and Two Different Methoxyaryl-Substituted Propylenes by Scandium Catalyst Makes Tough and Fast Self-Healing Elastomers", Angew. Chem. Int. Ed, 2021, DOI: 10.1002/anie.202111161 L. Jiang, X. Zhang, Y. Wang, F. Guo, Z. Hou, "N-Monomethylation of Amines with Methanol by Syndiotactic Poly(aminostyrene)-supported Palladium Nanoparticle Catalyst", Asian J. Org. Chem., 2021, Y. Wang, L. Jiang, X. Ren, F. Guo, Z. Hou, "Synthesis of bromine-functionalized polyolefins by scandium-catalyzed copolymerization of 10-bromo-1-decene with ethylene, propylene, and dienes", J Polym Sci., 2021, DOI: 10.1002/pol.20210488 K. Nishii, G. Zhou, Y. Saito, A. Yamamoto, M. Nishiura, Y. Luo, and Z. Hou, "Synthesis of Thermoplastic Elastomers by Yttrium-Catalyzed Isospecific Trans-1,4-Polymerization of (E)-1,3-Pentadiene", Bull. Chem. Soc. Jpn., 2021, 94, 1285–1291. (a special issue)DOI: 10.1246/bcsj.20210026 P. Wang, G. Luo, J. Yang, X. Cong, Z. Hou, and Y. Luo, "Theoretical Studies of Rare-Earth-Catalyzed [3 + 2] Annulation of Aromatic Aldimine with Styrene: Mechanism and Origin of Diastereoselectivity",J. Org. Chem., 2021, 86, 4236–4244. S. Lou, Q. Zhuo, M. Nishiura, G. Luo, and Z. Hou, "Enantioselective C–H Alkenylation of Ferrocenes with Alkynes by Half-Sandwich Scandium Catalyst",J. Am. Chem. Soc., 2021, 143, 2470-2476. DOI: 10.1021/jacs.0c13166 Y. Ma, S. Lou, and Z. Hou, "Electron-deficient boron-based catalysts for C–H bond functionalisation", Chem. Soc. Rev.,2021, 50, 1945-1967. DOI: 10.1039/d0cs00380h S. Hu, T. Shima, and Z. Hou,"Hydrodeoxygenative Cyclotetramerization of Carbon Monoxide by a Trinuclear Titanium Polyhydride Complex",J. Am. Chem. Soc., 2020, 142, 19889-19894.　DOI: 110.1021/jacs.0c10403　 Y. Zhao, G. Luo, X. Xu, Z. Hou and Y. Luo,"A computational study of the reactivity of rare-earth/phosphorus Lewis pairs toward polymerization of conjugated polar alkenes",Inorg. Chem. Front., 2020, 7, 4600-4610. 　DOI: 10.1039/d0qi01067g S. Lou, L. Zhang, Y. Luo, M. Nishiura, G. Luo, Y. Luo, and Z. Hou,"Regiodivergent C-H Alkylation of Quinolines with Alkenes by Half-Sandwich Rare-Earth Catalysts",J. Am. Chem. Soc., 2020. 　DOI: 10.1021/jacs.0c08362　 Z. Li, L. Zhang, M. Nishiura, G. Luo, Y. Luo, and Z. Hou,"Enantioselective Cyanoborylation of Allenes by N-Heterocyclic Carbene-Copper Catalysts",ACS Catal., 2020. 　DOI: 10.1021/acscatal.0c03018　 T. Shima, J. Yang, G. Luo, Y. Luo, and Z. Hou,"Dinitrogen Activation and Hydrogenation by C5Me4SiMe3-Ligated Di- and Trinuclear Chromium Hydride Complexes",J. Am. Chem. Soc., 2020, 142, 9007–9016. 　DOI: 10.1021/jacs.0c02939 J. Yang, G. Luo, Y. Yu, J. Qu, Z. Hou,Y. Luo,"Theoretical Mechanistic Insights into Dinitrogen Activation by a Diniobium Tetrahydride: Two-State Reactivity and the Role of Potassium Cation Promoter ",Inorg. Chem., 2020, 59, 4626–4633. https://doi.org/10.1021/acs.inorgchem.9b03733 X. Cong, G. Zhan, Z. Mo, M. Nishiura, and Z. Hou,"Diastereodivergent [3+2] Annulation of Aromatic Aldimines with Alkenes via C-H Activation by Half-Sandwich Rare-Earth Catalysts ",J. Am. Chem. Soc., 2020, 142, 5531−5537. 　DOI: 10.1021/jacs.0c01171　 F. Guo, L. Jiang, K. Diao and Z. Hou,"Stereoselective copolymerization of 4-(N,N-diphenylamino)styrene and isoprene by a C5H5-ligated scandium catalyst: synthesis of amino-functionalized crystalline styrenic thermoplastic elastomers",Polym. Chem., 2020, 11, 1314–1320. 　DOI: 10.1039/c9py01789e

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