研究生专题报告暨高济宇有机化学前沿讲座

发布时间:2016-04-06浏览次数:2265

题  目:Werner Complexes: A New Class of Chiral Hydrogen Bond Donor Catalysts for Enantioselective Organic Reactions

报告人:John A. Gladysz教授
        Department of Chemistry, Texas A&M University

时  间:2016年4月15号(星期五)下午16:00

地  点:仙林化学楼 H201报告厅

邀请人:强琚莉 副教授,王乐勇 教授

email:  gladysz@mail.chem.tamu.edu
Web: http://www.chem.tamu.edu/rgroup/gladysz/

    John A. Gladysz is a native of the Kalamazoo, Michigan area, and obtained his B.S. degree from the University of Michigan (1971) and his Ph.D degree from Stanford University (1974) with E. E. van Tamelen. He subsequently held appointments at UCLA (Assistant Professor, 1974-1982), the University of Utah (Associate Professor and Professor, 1982-1998), and the University of Erlangen-Nuremberg in Germany (Professor Ordinarius, 1998-2007). He then assumed the Dow Chair in Chemical Invention at Texas A&M University, where he is Distinguished Professor of Chemistry.
    Gladysz has been a fellow of the Alfred P. Sloan Foundation (1980-1984) and a Camille and Henry Dreyfus Teacher-Scholar Grant recipient (1980-1985). He received an Arthur C. Cope Scholar Award in 1988, the University of Utah Distinguished Research Award in 1992, the ACS Award in Organometallic Chemistry in 1994, a von Humboldt Foundation Research Award for Senior Scientists in 1995, the International Fluorous Technologies Award in 2007, the Texas A&M Distinguished Achievement Award in Research in 2013, and the Royal Society of Chemistry Award in Organometallic Chemistry in 2013. He was elected as a Fellow of the American Chemical Society in the inaugural year, 2009, and became a Fellow of the Royal Society of Chemistry in 2013.
    From June 1984 through July 2010, he served as the Associate Editor of Chemical Reviews. He then succeeded Dietmar Seyferth as the Editor in Chief of Organometallics, a position he held until January 2015.
    Gladysz has authored over 500 papers, book chapters, patents, and editorials, and his re­search spans a wide range of problems in the general areas of synthetic and mechanistic organomet­allic chemistry, and catalysis.
    On the personal side, he is married to Janet Blümel, a Professor of Chemistry at Texas A&M University who specializes in inorganic chemistry, supported catalysts, and solid state NMR spectroscopy. They live on the Crow's Nest Ranch, which consists of 137 acres (56 hectares) 4 miles east of College Station.
 
Abstract for Lecture:
 
    Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en)3]3+, and relat­ed species, have played important historical roles in the development of inorganic chemistry and stereochemistry.1,2 As Werner described in 1912, the two enantiomers, commonly desig­nated L and D, can be separated by crystallization of the diastereomeric tartrate salts.2 How­ever, despite the low cost and ready availability of the building blocks, there have been no ap­plications in enantioselective organic synthesis.
 
    We have found that [Co(en)3]3+ and related cations can be rendered soluble in organic solv­ents using lipophilic anions such as "BArf".3-5 Suitably functionalized derivatives are highly enantioselective catalysts for a variety of carbon-carbon bond forming reactions.4-6 The mech­anisms involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties. Other types of metal-containing chiral hydrogen bond donors are also effective, in­cluding a chelate of the CpRuL fragment.7,8
 
1 Kauffman, G. B. Coord. Chem. Rev. 1974, 12, 105.
2 Werner, A. Chem. Ber. 1911, 44, 1887 and 1912, 45, 121.
3 Ganzmann, C.; Gladysz, J. A. Chem. Eur. J. 2008, 14, 5397.
4 Lewis, K. G.; Ghosh, S. K.; Bhuvanesh, N.; Gladysz, J. A. ACS Central Science 2015, 1, 50.
5 GGhosh, S. K.; Ganzmann, C.; Bhuvanesh, N.; Gladysz, J. A. Angew. Chem. 2016, 128, in press.
6 Kumar, A.; Ghosh, S. K.; Gladysz, J. A. Org. Lett. 2016, 18, 760-763
7 Thomas, C.; Gladysz, J. A. ACS Catalysis 2014, 5, 1134.

8 (a) Scherer, A.; Mukherjee, T.; Hampel, F.; Gladysz, J. A. Organometallics 2014, 33, 6709. (b) Mukherjee, T.; Ganzmann, C.; Bhuvanesh, N.; Gladysz, J. A. Organometallics 2014, 33, 6723.