中国科学院兰州化学物理研究所所庆55周年学术报告
报告题目:Novel Tetraphosphorus Ligands for Highly Regioselective Liner Hydroformylation
报告人:张绪穆教授
报告时间:6月29日(星期六)上午10:00
报告地点:理化楼三楼多功能学术报告厅
报告人简介:
获得的奖项:独立工作以来发表了学术论文200多篇,H-index 60。其中大量论文发表在国际顶尖刊物如:科学(Science)、美国化学会志 (J. Am. Chem. Soc.)和德国应用化学(Angew. Chem. Int. Ed.)等杂志上,特别是关于不对称氢化领域的研究论文在国际上有重大的影响力,并在国内外获得众多奖项:2002年获得美国化学会 Arthur C. Cope Scholar 奖,是第一位获此殊荣的来自中国大陆的科学家;2011年荣获中国“十大经济创新人物”。
主要研究领域:1)发展高效、高选择性不对称催化反应手性配体工具箱;2)发展高效、高选择性的化学催化反应(不对称氢化、不对称氢甲酰化、线性氢甲酰化、酯基以及酰胺类化合物的绿色还原等);3)催化反应在重要的药物中间体和生物活性天然产物合成中的应用。
张绪穆教授在国家自然科学基金等的前期资助下,长期进行催化氢化反应的研究,在新型氢化催化剂的合成、结构和反应研究等方面都取得了创新性的成果。他发展的大量手性膦配体,对高效高选择性不对称催化氢化做出了很大的贡献(Acc. Chem. Res. 2007, 40, 1278;Chem. Rev. 2003, 103, 3029);并成功完成了多项手性药物的工业规模生产,推动了产学研结合向纵深发展。他设计合成的一系列刚性给电性的手性膦配体如TangPhos、DuanPhos和ZhangPhos,已成功应用于十分广泛的不对称催化氢化反应中(Angew. Chem. Int. Ed. 2010, 49, 6421; Angew. Chem.Int. Ed. 2009, 48, 6052; Angew. Chem. Int. Ed. 2007, 46, 2623; Angew. Chem. Int. Ed.2002, 41, 1612)。在C=C、C=O、C=N的不对称氢化还原领域中,作出了很多具有国际影响力的工作(Angew. Chem. Int. Ed. 2012, 51, 8573;Angew. Chem. Int. Ed. 2011, 50, 10679)。在手性配体设计及不对称氢化两大领域,张绪穆教授发表的论文、专利和报告在SCI-Finder Search中都名列世界前茅。
报告内容简介:
Regioselective hydroformylation is a powerful carbon-carbon bond forming reaction. From an industrial perspective, this reaction represents the largest homogeneous catalytic process with the annual yield of over 10 million tons of oxo products worldwide per year since its first discovery by Otto Roelen in 1938, due to readily availability of cheap feedstocks in huge amount such as propene and butene and other unsaturated olefins. Most commercial hydroformylation processes use highly reactive rhodium catalysts that are modified with either mono- or bisphosphorus ligands to address the issue of regio- and stereoselectivity. Phosphane- and phosphite-based systems giving highly regioselective linear aldehydes have been reported. Some elegant examples include Bisbi Xantphos, Biphephos, Naphos,calyx arene bisphos-phite, pyrrole-based bisphosphoramidite, and self-assembled bisphosphane. In spite of that a number of ligands have been developed, high catalyst loading, low reaction rate, poor selectivity and narrow substrate scope are still unsolved problems in hydroformylation processes. By incorporating four chelating phosphine atoms, our group recently developed two tetraphosphorus ligands which achieved unprecedented regioselectivity for the hydroformylation of terminal and internal olefins. To the best of our knowledge, the regioselectivity achieved utilizing the tetraphosphorus ligands is the highest.
Novel tetraphosphorus ligandsdeveloped by Zhang group
References
1.G.. Liu, K. Huang, B. Cao, M. Chang, S. Li, S. Yu, L. Zhou, W. Wu, and X. Zhang, Org. Lett.2012, 14, 102–105
2.X. Zheng, B. Cao, T. Liu, X. Zhang. Adv. Synth. Catal. 2013, 355, 679-684.
3.S. Li, K. Huang, J. Zhang, W. Wu, X. Zhang. Org. Lett. 2013, 15, 1036–1039.
4.C. Chen, Y. Qiao, H. Geng, X. Zhang. Org. Lett. 2013, 15, 1048-1051.
5.K. Huang, S. Li, M. Chang, X. Zhang. Org. Lett. 2013, 15, 484-487.
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