Noyori Catalytic Asymmetric Hydrogenation Wang jiahao [email protected].
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Transcript of Noyori Catalytic Asymmetric Hydrogenation Wang jiahao [email protected].
Description
R1 R2
R3 R4
R5 R6
R1 R2
R3
R4
R6 R5
OHO
functionalized ketone
functionalized olef in
H2, (R)- or (S)- LigandMetal [Ru(II) or Rh(I)]
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
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
72% ee
DIOP
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.
Monsanto L-DOPA process.
S/C=20000:1
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.
H
C6H5
CN
NHCOC6H5
H
C6H5
NHCOCH3
CH3
H
C6H5
COOC2H5
NHCOOC2H5
H
C6H5
COOH
CH3
Tridentate substrates:
Bidentate substrates:
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.
PPh2
PPh2
(R)-BINAP
1
1'
2
2'
CO2H
NHCOPh
(R)-BINAP-Rh, H2, EtOHCO2H
NHCOPh
S, 97% yield, >99% ee
S/C (W) =100, 4 atm, rt., 48 h
Synthesis of BINAP 1980
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 1986
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.
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
HO2C NHCOPh
Sub
NHO
Ph
CO2H
(P-P)Rh
NH
OPh
CO2H
(P-P)(H)SRh
HHO2C
H
NHCOPh
HS
ONH
CO2H
Ph
(P-P)Rh
HO2C
H
NHCOPh
H R
(P-P)(H)SRh
H
NH
PhO
CO2H
H2
H2
major
minor
[(P-P)RhS2]+
NHO
Ph
CO2H
(P-P)(H)2Rh
ONH
CO2H
Ph
(P-P)(H)2Rh
S
S
S
S
2S
2S +
+
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
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.
CO2Me
NHCOMe
CO2Me
NHCOMe
> 99% yield, > 92% ee
(R)-BINAP-Ru, H2
Functionalized olefins including enamides, α, β- and α, γ-unsaturated carboxylic acids, allylic and homoallylic alcohols , as well as various functionalized ketones.
Kitamura, Masato; Nakatsuka, Hiroshi. Chem. Commun. 2011, 842-846.
Unsaturated monohydride mechanism
R OMe
O O
R OMe
OOH
> 99% ee
(R)-BINAP-Ru, H2
RuX2(B1NAP), [RuX(BINAP)(arene)]Y
X=Cl, Br, I; Y=halogen or BF4-
S/C up to 10,000
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, 1208-1210.
Variations and Improvements
Q
Q
R3
PR12R2
R3
PR12R2
N
N
OCH3
H3CO
OCH3
H3CO
(R)-P-Phos
P
P
N
N
OCH3
H3CO
OCH3
H3CO
P
P
(R)-xyl-P-Phos
N
N
OCH3
H3CO
OCH3
H3CO
P
P
(R)-Tol-P-Phos
H3CO
H3CO
P
P
(R)-MeO-Biphep
Tang, W.; Chi, Y.; Zhang, X. Org. Lett. 2002, 4, 1695-1698.
Suzuki couplingUllmann coupling(+)-DTTA=(+)-(2R,3R)-2,3-o-ditoluoyltartric acid
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.
R1 R2
O
SEGPHOS Series
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.
DTBM-SEGPHOS
Synthetic Utility
1. Hydrogenation of dehydroamino acid derivatives
Sub= (Z)- or (E)-α-(acylamino)acrylic acids or esters
Burk, M. J.; Feaster, J. E.; Nugent, W. A,; Harlow, R. L. J. Am. Chem. Soc. 1993, 115, 10125-10138.
DuPhos
NHAc
CO2Me
NHAc
CO2Me
CO2Me
NHAcor
(R,R)-Pr-DuPhos-Rh, H2Z
E
99.6% ee
99.4% eeR
NHAc
CO2Me
NHAc
CO2MeCO2Me
or
(R,R)-Pr-DuPhos-Rh
Z
E
(R,R)
D2
H D
AcHN D
CO2Me
D H
HAcHN D
(S,R)
Isomerization
Burk, M. J.; Feaster, J. E.; Nugent, W. A,; Harlow, R. L. J. Am. Chem. Soc. 1993, 115, 10125-10138.
NHAc
CO2Me(R,R)-Me-BPE-Rh
H2
NHAc
CO2Me
98.2% ee
Sub= β, β - disubstituted α-dehydroamino acids or esters
NHAc
CO2Me
Me
(R,R)-Me-BPE-Rh
H2NHAc
CO2Me
Me
90.6% ee
Ph Ph
Burk, M. J.; Bedingfield. K. M.; Kiesman, W. F.; Allen, J. G. Tetrahedron Lett. 1999, 40, 3093-3096.
(S,S)-Me-BPE
Burk, M. J.; Bedingfield. K. M.; Kiesman, W. F.; Allen, J. G. Tetrahedron Lett. 1999, 40, 3093-3096.
NHAc
CO2Me
R1
R2
(2Z, 4E) - SubEntries 1-8
CO2Me
NHAc
R1
R2
(2E, 4E) - SubEntries 9-14
3. Hydrogenation of ( β-acylamino) acrylates
BINAP, DuPhos, BICP, BDPMI and MalPHOScatalyst: (S)-XylyI-o-BINAPO-Ru, (99% ee)catalyst: (S,S,R,R)-TangPhos-Rh, (93.8% ee)
Tang, W.; Zhang, X. Org. Lett. 2002, 4, 4159-4161.
TangPhos
Up to 99.6% ee
Ru-Me-DuPhos, 87.8% eeRh-BICP, 86.9% eeRu-BINAP, 5% ee
TON=200
Tang, W.; Zhang, X. Org. Lett. 2002, 4, 4159-4161.
4. Hydrogenation of enol esters
OAc
R' H2
Catalyst
OAc
R'
catalyst: (R,R)-Et-DuPhos-Rh, 61 (>99% ee, R-confign., R' = CO2Et) catalyst: (S)-Cz-TunaPhos-Ru, 61 (97.7% ee, S-conf ign., R'= I-Np)
Wu, S.; Wang, W.; Tang, W.; Lin, M.; Zhang, X.; Org. Lett. 2002, 4, 4495-4497.