化学家的故事

• What is metathesis? meta means change thesis means position
Scheme 1
In short
AB + CD → AC + BD
Nobel Prize in Chemistry 2005
A Variety of Olefin Metathesis Reactions
Year 1912 Laureates Victor Grignard Paul Sabatier Otto Paul Hermann Diels Kurt Alder Herbert C. Brown Georg Wittig William S. Knowles Ryoji Noyori K. Barry Sharpless Yves Chauvin Robert H. Grubbs Richard R. Schrock Contributions for the discovery of the so-called Grignard reagent for their discovery and development of the diene synthesis Phosphorus ylide
1950
1979
2001
Chirally catalysed hydrogenation Chirally catalysed oxidation Development of the metathesis method
2005
Nobel Prizes for synthetic methodologies
Schrock’s Catalysts
(a) J.S. Murdzek and R.R. Schrock., Organometallics,12,6, 1373 (1987). (b) R.R. Schrock, S.A. Krouse, K. Knoll, J. Feldman, J.S. Murdzek and D.C. Yang, J. Mol. Catal., 46, 243 (1988). (c) R.R. Schrock, J.S. Murdzek, G.C. Barzan, J. Robbins, M. DiMare and M. O`Regan, J. Am. Chem. Soc., 112, 3875 (1990). (d) G.C. Bazan, J.H. Oskam, H.-N. Cho, L.Y. Park and R. R. Schrock, J. Am. Chem. Soc., 113, 6899 (1991).
Yves Chauvin 1/3 of the prize France Institut Franç du ais Pé trole Rueil-Malmaison, France b. 1930
Robert H. Grubbs 1/3 of the prize USA California Institute of Technology (Caltech) Pasadena, CA, USA b. 1942
Nobel Prizes for synthetic methodologies
Otto Paul Hermann Diels 1/2 of the prize Federal Republic of Germany Kiel University Kiel, Federal Republic of Germany b. 1876 d. 1954
Ziegler, K.; Holzkamp, E.; Breil, H.; Martin, H. Angew. Chem. Int. Ed. 1955, 67, 541.
Nobel Prize in Chemistry 2005
Explanation of the Mechanism
WRONG TURNS
1950
Kurt Alder 1/2 of the prize Federal Republic of Germany Cologne University Cologne, Federal Republic of Germany b. 1902 d. 1958
ห้องสมุดไป่ตู้
O +
O
base
O
aldol O condesation
2001
USA
The Scripps Research Institute La Jolla, CA, USA b. 1941
The Nobel Prize in Chemistry 2005
"for the development of the metathesis method in organic synthesis"
O witting reaction
CH3MgBr OH
acid -H2O
Nobel Prizes for synthetic methodologies
William S. Knowles 1/4 of the prize USA St. Louis, MO, USA b. 1917 Ryoji Noyori 1/4 of the prize Japan Nagoya University Nagoya, Japan b. 1938 K. Barry Sharpless 1/2 of the prize
Unusual intermediates proposed initially have since been rejected!
Nobel Prize in Chemistry 2005
Mechanism Proposed by Chauvin
Chauvin's work gave the field a chance to move away from its state of alchemy, although it took several years before the mechanism was experimentally supported and widely accepted.
Development of the metathesis method in organic synthesis
——The Nobel Prize in Chemistry 2005
Mo Fanyang April 23th, 2006 The Group of ZZM
Nobel Prizes for synthetic methodologies
Nobel Prize in Chemistry 2005
Grubbs catalysts
R.H. Grubbs and T.K Brunck, J. Am. Chem. Soc., 94, 2538 (1972). (b) B.M. Novak and R.H. Grubbs, J. Am. Chem. Soc., 110, 960 (1988). (c) S.T. Nguyen, L.K. Johnsson, and R.H. Grubbs, J. Am. Chem. Soc., 114, 3974 (1992). (d) Z. Wu, S.T. Nguyen, R.H. Grubbs and J.W. Ziller, J. Am. Chem. Soc., 117, 5503 (1995). (e) S.T. Nguyen, R.H. Grubbs,J.W. Ziller, J. Am. Chem. Soc., 115, 9858 (1993). (f) G.C. Fu, S.T. Nguyen, R.H. Grubbs, J. Am . Chem. Soc., 115, 9856 (1993). (g) P. Schwab, M.B. France and J.W. Ziller, R.H. Grubbs, Angew. Chem., Int. Ed. Engl., 34, 2039 (1995), Angew. Chem. 107, 2179 (1995). (h) P. Schwab, R.H. Grubbs and J.W. Ziller, J. Am. Chem. Soc. 118, 100 (1996). (i) M. Scholl, T.M. Trnka, J.P. Morgan and R.H. Grubbs, Tetrahedron Lett. 40, 2247 (1999).
Victor Grignard 1/2 of the prize France Nancy University Nancy, France b. 1871 d. 1935
1912
Paul Sabatier 1/2 of the prize France Toulouse University Toulouse, France b. 1854 d. 1941
OH
O
X
Y
Robinson Annelation Reaction
X,Y = COOH, OH, NH2, COCl ……
( )n
R1 + R2 R4 R2 R4 R3 R1 R3
R1 R2 R3
R4
Nobel Prizes for synthetic methodologies
1979
Herbert C. Brown
Calderon, N.; Chen, H. Y.; Scott, K. W. Olefin Metathesis A Novel Reaction for Skeletal Transformations of Unsaturated Hydrocarbons. Tetrahedron Lett. 1967, 34, 3327-3329.
Nobel Prize in Chemistry 2005
The discovery of olefin metathesis reaction
• The Advent of Olefin Metathesis by Industrial Researchers
1956 H. S. Eleuterio, at Du Pont's petrochemicals department 1960 W. L. Truett et al. at Du Pont’s polychemicals department 1964 R. L. Banks et al. at Phillips Petroleum 1967 N. Caldron et al. at Goodyear Tire & Rubber
by K. C. Nicolaou
J.-L. Hérisson and Y. Chauvin, Makromol. Chem., 141, 161 (1971).
Nobel Prize in Chemistry 2005
Catalysts for metathesis
MoO3/ SiO2,Re2O7/Al2O3,WCl6/Bu4Sn
Nobel Prize in Chemistry 2005
Ziegler Catalysts
Not only did Ziegler’s discovery of metalcatalyzed olefin polymerizations forever change polymer science, but also the science surrounding it supplied the motivation for many areas of modern organometallic chemistry research. by Robert H. Grubbs
Richard R. Schrock 1/3 of the prize USA Massachusetts Institu te of Technology (MI T) Cambridge, MA, U SA b. 1945
Nobel Prize in Chemistry 2005
Introduction
1/2 of the prize USA Purdue University West Lafayette, IN, USA b. 1912 (in London, United Kingdom) d. 2004 Georg Wittig 1/2 of the prize Federal Republic of Germany University of Heidelberg Heidelberg, Federal Republic of Germany b. 1897 d. 1987