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Noyori assymetric hydrogenation
Noyori Asymmetric Hydrogenation is a chemical reaction used to hydrogenate ketone and olefin. This reaction requires a chiral ruthenium complex catalyst introduced by Ryoji Noyori in 1987[1]. He won the Nobel Prize in Chemistry in 2001 for his study of the asymmetric hydrogenation. Two different types ruthenium catalyst are used. BINAP-Ru catalyst system is used for the asymmetric hydrogenation of olefins [2]. BINAP/diamine-Ru catalyst system is used for the asymmetric hydrogenation of ketones [3]. Due to its high stereoselectivity and reactivity, Noyori Asymmetric hydrogenation is widely used to make drugs such as naproxen, morphine, levofloxacin, and etc.[4,5,6,7]

BINAP-Ru
Before Noyori invented BINAP-Ru catalyst system, rhodium catalyst was conventionally used for the catalytic hydrogenation of olefins [8,9]. Rh catalyst could achieve high ee, but the reaction was relatively slow and only worked under specific condition [10,11]. The scope of the reaction was also limited to the synthesis of amino acid. The invention of the BINAP ligand and the use of Ru, instead of Rh, enabled the faster reaction under milder condition with wider range of scope.

In 1986, Noyori and coworkers discovered the BINAP-Ru dicarboxylate catalyst. This complex catalyzed asymmetric hydrogenation of some olefin [2]. While the Rh catalysts go through +1/+3 redox process, the Ru catalysts go through monohydride intermediate without redox process. The catalytic reaction proceeds via the coordination of the functional group to the Ru center [12]. NEED TO DRAW THE TRANSITION STATE

This BINAP-Ru dicarboxylate is widely used in the pharmaceutical industry. The applications are summarized in the scheme below.

A BINAP-Ru system can also be used for the hydrogenation of C=O bond [13]. While the BINAP-Ru dicarboxylate is not effeicient to hydrogenate C=O bond, the BINAP-Ru dihalide can effectively catalyze the C=O bond. Stereoselectivity is achieved and predicted from the coordinative N,O, or X near the C=O bond [14].

Applications

BINAP/diamine-Ru
Used in hydrogenation of simple ketones[3]

Transition state vs Six membered transition state better than 4 membered transition state. R. Noyori, T. Ohkuma, Angew. Chem. 2001, 113, 41; Angew. Chem. Int. Ed. 2001, 40, 40. R. Noyori, M. Koizumi, D. Ishii, T. Ohkuma, Pure Appl. Chem. 2001,73, 227.

Transition state from top view

Ph/ph steric hindered. Less hindered

Mechanism a) K. Abdur-Rashid,M. Faatz, A. J. Lough, R. H. Morris, J. Am. Chem. Soc. 2001,123, 7473 b) R. Hartmann, P. Chen, Angew. Chem. 2001, 113, 3693; Angew. Chem. Int. Ed. 2001, 40, 3581.

Reference
(1)Noyori, R., Okhuma, T.; Kitamura, M.; Takaya, H.; Sayo, N.; Kumobayashi, H.; Akuragawa, S. J. Am. Chem. Soc. 1987, 109, 5856–5858.

(2) R. Noyori, M. Ohta, Y. Hsiao, M. Kitamura, T. Ohta, H. Takaya, J. Am. Chem. Soc. 1986, 108, 7117.   a) T. Ohta, H. Takaya, R. Noyori, Inorg. Chem. 1988, 27, 566;     b) M.Kitamura, M. Tokunaga, R. Noyori, J. Org. Chem. 1992, 7, 4053;   c) H. Takaya, T. Ohta, S. Inoue, M. Tokunaga, M. Kitamura, R.Noyori, Org. Synth. 1993, 72, 74.

(3) a) R. Noyori, T. Ohkuma, Angew. Chem. 2001, 113, 41; Angew. Chem. Int. Ed. 2001, 40, 40.   b) R. Noyori, T. Ohkuma, Pure Appl. Chem. 1999, 71, 1493.   c) R. Noyori, M. Koizumi, D. Ishii, T. Ohkuma, Pure Appl. Chem. 2001,73, 227.

(4) T. Ohta, H. Takaya, M. Kitamura, K. Nagai, R. Noyori, J. Org. Chem. 1987, 52, 3174.

(5) M. Kitamura, M. Yoshimura, M. Tsukamoto, R. Noyori, Enantiomer 1996, 1, 281.

(6) M. Kitamura, I. Kasahara, K. Manabe, R. Noyori, H. Takaya, J. Org. Chem. 1988, 53, 708.

(7)

(8)[33] An early example of phosphane } Ru-complex-catalyzed hydrogenation: P. S. Hallman, B. R. McGarvey,G.Wilkinson, J. Chem. Soc. A 1968, 3143.

(9) Ru-catalyzed asymmetric hydrogenation of olefins was first achieved using a DIOP }Ru complex: B. R. James, D. K. W.Wang, R. F. Voigt, J. Chem. Soc. Chem. Commun. 1975, 574.

[10] A. Miyashita, A. Yasuda, H. Takaya, K. Toriumi, T. Ito, T. Souchi, R. Noyori, J. Am. Chem. Soc. 1980, 102, 7932.

[11] a) A. Miyashita, H. Takaya, T. Souchi, R. Noyori, Tetrahedron 1984, 40, 1245; b) K. J. Brown, M. S. Berry, K. C. Waterman, D. Lingenfelter, J. R. Murdoch, J. Am. Chem. Soc. 1984, 106, 4717.

[12] a) T. Ohta, H. Takaya, R. Noyori, Tetrahedron Lett. 1990, 31, 7189; b) M. T. Ashby, J. Halpern, J. Am. Chem. Soc. 1991, 113, 589.

[13] a) M. Kitamura, M. Tokunaga, T. Ohkuma, R. Noyori, Tetrahedron Lett. 1991, 32, 4163; b) M. Kitamura, M. Tokunaga, T. Ohkuma,R.Noyori, Org. Synth. 1993, 71, 1; c) K. Mashima, K. Kusano, N. Sato, Y.Matsumura, K. Nozaki, H. Kumobayashi, N. Sayo, Y. Hori, T.Ishizaki, S. Akutagawa, H.Takaya, J. Org. Chem. 1994, 59, 3064.

[14] a) M. Kitamura, T. Ohkuma, S. Inoue, N. Sayo, H. Kumobayashi, S.Akutagawa, T. Ohta, H. Takaya, R. Noyori, J. Am. Chem. Soc. 1988,110, 629; b) K. Mashima, K. Kusano, T. Ohta, R. Noyori, H. Takaya,J. Chem. Soc. Chem. Commun. 1989, 1208; c) T. Ohkuma, M.Kitamura, R. Noyori, Tetrahedron Lett. 1990, 31, 5509.