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1. 锆催化的三甲基铝对烯烃的不对称加成以及它在天然产物合成中的应用. Negishi教授研究组于1995年发现了锆催化的三甲基铝对烯烃的不对称加成反应。该反应是世界金属有机化学,有机不对称合成化学的前沿课题之一。在谭泽博士以及另两位组员的怒力下,该反应被成功地应用在天然产物合成中。2005年发展的一锅煮法,一步一循环合成一个不对称手性碳中心对于deoxypolypropionates一类天然产物的合成有突破性的意义。其他所有的方法皆要求至少3 步. 其成果的价值在一系列的天然产物以及天然产物片段(TMC-151-A-F partial structure, Scyphostatin side-chain, siphonarienal, siphonarinone, siphonarielonone, ionomycin, borrellidin, doliculide partial structure)的合成中得到了充份的体现。以上所有的天然产物都有一定的生物活性. 他们的合成方法的改进对于合成此类天然化合物的衍生物以便找到更有效的药物有重大意义. 2. 钯催化的偶联反应以及它们在天然产物合成中的应用。 (i) 在德国应用化学杂志上报道了钯催化的烷基锌试剂与1,1-二氯-1-烯烃的偶联反应,可以选择性的得到顺式或者反式三取代烯烃。顺式三取代烯烃合成困难较大,正常反应条件一般得到反式三取代烯烃。此新成果提出了一个选择性合成顺式三取代烯烃的新方法。该文章被Oliver Reiser教授在德国应用化学杂志上(2006,2838-2840)重点介绍。 (ii) 钯催化得 α-iodoenones 与有机锌试剂的偶联并合成了天然产物(+)-harveynone和天然产物 (+)-tricholomenyne A, (+)-epolactaene. 其中天然产物 (+)-epolactaene的合成为美国卫生所项目中子项目.

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Zirconium-Catalyzed Asymmetric Carboalumination of Alkenes(ZACA)-Lipase-Catalyzed Acetylation Synergy, Huang, Z.; Tan, Z.; Novak, T.; Zhu, G.; Negishi, E. Adv. Synth. Catal. 2007, 539-545。. Selective Synthesis of Epolactaene Featuring Efficient Construction of Methyl (Z)-2-Iodo-2-butenoate and (2R,3S,4S)-2-Trimethylsilyl-2,3-epoxy-4-methyl-g-butyrolactone, Tan, Z.; Negishi, E. Org. Lett. 2006, 8, 2783-2785. ZACA Reaction: Zr-Catalyzed Asymmetric Carboalumination of Alkenes,Liang, B.; Novak, T.; Tan, Z.; Negishi, E. Asymmetric Synthesis-The Essentials, Wiley-VCH, Weinheim, 2006, in press. Zirconium-catalyzed Asymmetric Carboalumination (ZACA Reaction) of 1,4-dienes, Tan, Z.; Liang, B.; Huo, S.; Shi, J.; Negishi, E. Tetrahedron: Asymmetry 2006, 17,512-515. Widely Applicable Pd-catalyzed trans-selective Monoalkylation of Unactivated 1,1-Dichloro-1-alkenes and Pd-Catalyzed Second Substitution for the Selective Synthesis of E or Z Trisubstituted Alkenes, Tan, Z.; Negishi, E. Angew. Chem. Int. Ed. 2006, 45, 762-765. (selected as a hot paper, highlighted in 2006ACIE2838). Catalytic, Efficient, and syn-Selective Construction of Deoxypolypropionates and Other Chiral Compounds via Zr-Catalyzed Asymmetric Carboalumination of Allyl Alcohol, Liang, B.; Novak, T.; Tan, Z.; Negishi, E. J. Am. Chem. Soc. 2006, 128, 2770-2771. All-catalytic, Efficient and Asymmetric Synthesis of α,ω-Diheterofunctional Reduced Polypropionates via “One-pot” Zr-catalyzed Asymmetric Carboalumination-Pd-catalyzed Cross-coupling Tandem Process, Novak, T.; Tan, Z.; Liang, B.; Negishi, E. J. Am. Chem. Soc. 2005, 127, 2838-2839. An Efficient and General Method for the Synthesis of α,ω-Difunctional Reduced Polypropionates by Zr-catalyzed Asymmetric Carboalumination: Synthesis of the Scyphostatin Sidechain, Tan, Z.; Negishi, E. Angew. Chem. Int. Ed. 2004, 43, 2911-14. A New, Efficient, and General Route to Reduced Polypropionates via Zr-Catalyzed Asymmetric C-C Bond Formation, Negishi, E.; Tan, Z. Liang, B.; Novak, T. Proc. Natl. Acad. Sci. USA, 2004, 101, 5782-87. Efficient and Selective Synthesis of Siphonarienolone and Related Reduced Polypropionates via Zr-Catalyzed Asymmetric Carboalumination, Magnin-Lachaux, M.; Tan, Z.; Negishi, E. Org. Lett. 2004, 6, 1425-27. Palladium- or Nickel-Catalyzed Cross-Coupling with Organometals Containing Zinc, Aluminum, and Zirconium: The Negishi Coupling, Negishi, E.; Zeng, X.; Tan, Z.; Qian, M.; Hu, Q.; Huang, Z. Metal-Catalyzed Cross-coupling Reactions, de Meijere, A.; Diederich, F., Eds. Wiley-VCH, 2004, Chap. 15, p. 815-889. Diastereoselective, Enantioselective and Regioselective Carboalumination Reactions Catalyzed by Zirconocene Derivatives,Negishi, E.; Tan, Z. Topics in Organometallic Chemistry, Takahashi, T., Ed., Springer, 2004, 8,139-176. Synthesis of Natural Products via Palladium-Catalyzed Cross-Coupling,Tan, Z.; Negishi, E. In The Handbook of Organopalladium Chemistry for Organic Synthesis, Negishi, E., Ed., J. Wiley & Sons, New York, 2002, Sect. III.2.18, 863-942. Strictly Regiocontrolled α-Monosubstitution of Cyclic Carbonyl Compounds with Alkynyl and Alkyl Groups via Pd-Catalyzed Coupling of Cylclic α-Iodoenones with Organozincs, Negishi, E.; Tan, Z.; Liou, S-Y.; Liao, B. Tetrahedron 2000, 56, 10197-10207.

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