Transcript 40 - Wanbin Zhang Lab

Noyori Catalytic Asymmetric
Hydrogenation
Wang jiahao
[email protected]
Description
 Pharmaceuticals
 Agrochemicals
 Flavors
 Other fine
chemicals
President, RIKEN & University Professor, Nagoya University
Birth:
Kobe, Japan; 1938.
Education:
Bachelor: Kyoto University (Professor K. Sisido), 1961.
Master: Kyoto University (Professor K. Sisido), 1963.
Ph.D.: Kyoto University (Professor H. Nozaki), 1967.
Postdoctoral Fellow: Harvard University (Professor E. J. Corey),
1969–1970.
Publications:
Over 500 (original papers, reviews, chapters, commentaries,
and monographs).
ISI citations, ca. 35,000; h-index, 101.
Patents:
Over 250.
Historical Perspective
Mechanism
Variations and Improvements
Synthetic utility
Historical Perspective
Knowles, W. S.; Sabacky, M. J. Chem. Commun. 1968, 1445-1446.
Horner, L.; Siegel, H.; BUthe, H. Angew. Chem. Int. Ed. Engl. 1968, 7, 942.
Dang, T. P.; Kagan, H. B. J. Chem. Soc. Chem. Commun. 1971, 481.
3-15% ee
DIOP
72% ee
Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D. J. Chem. Soc. Chem. Commun. 1972, 10-11.
Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L. Weinkauff, D. J. J. Am. Chem.
Soc. 1977, 99, 5946-5952.
Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D. J. Chem. Soc. Chem. Commun. 1972, 10-11.
Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L. Weinkauff, D. J. J. Am. Chem.
Soc. 1977, 99, 5946-5952.
S/C=20000:1
Monsanto L-DOPA process.
Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D. J. Chem. Soc. Chem. Commun. 1972, 10-11.
Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L. Weinkauff, D. J. J. Am. Chem.
Soc. 1977, 99, 5946-5952.
Knowles, W. S.; Sabacky, M. J.; Vineyard, B. D. J. Chem. Soc. Chem. Commun. 1972, 10-11.
Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L. Weinkauff, D. J. J. Am. Chem.
Soc. 1977, 99, 5946-5952.
Miyashita, A.; Yasuda, A.; Takaya, H.; Toriumi, K.; Ito, T.; Souchi, T.; Noyori, R. J. Am. Chem. Soc.
1980, 102, 7932-7934.
Miyashita, A.; Yasuda, A.; Takaya, H.; Toriumi, K.; Ito, T.; Souchi, T.; Noyori, R. J. Am. Chem. Soc. 1980,
102, 7932–7934.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
Synthesis of BINAP 1980
Takaya, H.; Mashima, K.; Koyano, K.; Yagi, M.; Kumobayashi, H.; Taketomi, T.; Akutagawa, S.; Noyori, R.
J. Org. Chem. 1986, 51, 629–635.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
Synthesis of BINAP 1986
Sayo, N.; Zhang, X.; Ohmoto, T.; Yoshida, A.; Yokozawa, T. Eur. Patent 0,771,812, 1997.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
Synthesis of BINAP 1997
Mechanism
Burk, M. J. Acc. Chem. Res. 2000, 33, 363-372.
van den Berg, M.; Minnaard, A. J.; Schudde, E. P.; van Esch, J.; deVries, A. H. M.; deVries, J. G.; Feringa, B. L. J. Am. Chem. Soc. 2000, 122,
11539-11540.
Claver, C.; Fernandez, E.; Gillon, A,; Heslop, K.; Hyett, D. J.; Martorell, A,; Orpen, A. G.; Pringle, P. G. Chem. Commun. 2000, 961-962.
Reetz, M. T.; Mehler, G. Angew. Chem. Int. Ed. 2000, 39, 3889-3890.
Gridnev, 1. D.; Higashi, N.; Asakura, K.; Imamoto, T. J. Am. Chem. Soc. 2000, 122, 7183-7194.
DuPhos
Unsaturated dihydride mechanism
Ohta, T.; Takaya, H.; Noyori, R. Inorg. Chem. 1988, 27, 566-569.
Kitamura, M.; Tokunaga, M.; Noyori, R. J. Org, Chem. 1992, 57, 4053-4054.
Functionalized olefins including enamides, α, β- and α, γ-unsaturated carboxylic
acids, allylic and homoallylic alcohols，as well as various functionalized
ketones.
Kitamura, M.; Tokunaga, M.; Noyori, R. J. Org, Chem. 1992, 57, 4053-4054.
Kitamura, Masato; Nakatsuka, Hiroshi. Chem. Commun. 2011, 842-846.
Unsaturated monohydride mechanism
Wiles, J. A.; Bergens, S. H.; Young, Y. G. J. Am. Chem. Soc. 1997, 119, 2940-2941.
Noyori, R.; Ohkuma, T.; Kitamura, M.; Takaya, H.; Sayo, N.; Kumobayashi, H.; Akutagawa, S. J. Am.
Chem. Soc. 1987, 109, 5856-5858.
Mashima. K.; Kusano, K.; Ohta, T.; Noyori, R.; Takaya, H. J. Chem. Soc. Chem. Commun. 1989, 12081210.
Variations and Improvements
Tang, W.; Chi, Y.; Zhang, X. Org. Lett. 2002, 4, 1695-1698.
Tang, W.; Chi, Y.; Zhang, X. Org. Lett. 2002, 4, 1695-1698.
Suzuki coupling
Ullmann coupling
(+)-DTTA=(+)-(2R,3R)-2,3-oditoluoyltartric acid
Tang, W.; Chi, Y.; Zhang, X. Org. Lett. 2002, 4, 1695-1698.
S/C=100:1
S/C=2000:1
Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi, T.; Sayo, N.; Miura, T.; Kumobayashi, H. Adv. Synth. Catal.
2001, 343, 264–267.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi, T.; Sayo, N.; Miura, T.; Kumobayashi, H. Adv. Synth. Catal.
2001, 343, 264–267.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi, T.; Sayo, N.; Miura, T.; Kumobayashi, H. Adv. Synth. Catal.
2001, 343, 264–267.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
Shimizu, H.; Nagasaki, I.; Saito, T. Tetrahedron 2005, 61, 5405–5432.
Shimizu, Hideo; Nagasaki, Izuru; Matsumura, Kazuhiko; Sayo, Noboru; Saito, Takao. Acc. Chem. Res.
2007, 40, 1385–1393.
SEGPHOS Series
DTBM-SEGPHOS
Synthetic Utility
1. Hydrogenation of dehydroamino acid derivatives
Sub= (Z)- or (E)-α-(acylamino)acrylic acids or esters
DuPhos
Burk, M. J.; Feaster, J. E.; Nugent, W. A,; Harlow, R. L. J. Am. Chem. Soc. 1993, 115, 10125-10138.
Burk, M. J.; Feaster, J. E.; Nugent, W. A,; Harlow, R. L. J. Am. Chem. Soc. 1993, 115, 10125-10138.
Sub= β, β - disubstituted α-dehydroamino acids or esters
(S,S)-Me-BPE
Burk, M. J.; Bedingfield. K. M.; Kiesman, W. F.; Allen, J. G. Tetrahedron Lett. 1999, 40, 3093-3096.
Burk, M. J.; Bedingfield. K. M.; Kiesman, W. F.; Allen, J. G. Tetrahedron Lett. 1999, 40, 3093-3096.
2. Hydrogenation of enamides
99.5% ee
99% ee
3. Hydrogenation of ( β-acylamino) acrylates
BINAP, DuPhos, BICP, BDPMI and MalPHOS
catalyst: (S)-XylyI-o-BINAPO-Ru, (99% ee)
catalyst: (S,S,R,R)-TangPhos-Rh, (93.8% ee)
TangPhos
Up to 99.6% ee
Tang, W.; Zhang, X. Org. Lett. 2002, 4, 4159-4161.
TON=200
Ru-Me-DuPhos, 87.8% ee
Rh-BICP, 86.9% ee
Ru-BINAP, 5% ee
Tang, W.; Zhang, X. Org. Lett. 2002, 4, 4159-4161.
4. Hydrogenation of enol esters
Wu, S.; Wang, W.; Tang, W.; Lin, M.; Zhang, X.; Org. Lett. 2002, 4, 4495-4497.
TON=100
Wu, S.; Wang, W.; Tang, W.; Lin, M.; Zhang, X.; Org. Lett. 2002, 4, 4495-4497.
5. Hydrogenation of α-β unsaturated carbonyls
6. Hydrogenation of unsaturated alcohols
谢 谢！