noyori catalytic asymmetric hydrogenation wang jiahao [email protected]

39
Noyori Catalytic Asymmetric Hydrogenation Wang jiahao [email protected]

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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

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

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, M.; Tokunaga, M.; Noyori, R. J. Org, Chem. 1992, 57, 4053-4054.

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.

Tang, W.; Chi, Y.; Zhang, X. Org. Lett. 2002, 4, 1695-1698.

Suzuki couplingUllmann coupling(+)-DTTA=(+)-(2R,3R)-2,3-o-ditoluoyltartric 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.

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

2. Hydrogenation of enamides

99% ee

99.5% ee

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.

Wu, S.; Wang, W.; Tang, W.; Lin, M.; Zhang, X.; Org. Lett. 2002, 4, 4495-4497.

TON=100

5. Hydrogenation of α-β unsaturated carbonyls

6. Hydrogenation of unsaturated alcohols

谢 谢!