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Volumn 27, Issue 7, 2008, Pages 1514-1523

Origin of enantioselective hydrogenation of ketones by RuH 2(diphosphine)(diamine) catalysts: A theoretical study

Author keywords

[No Author keywords available]

Indexed keywords

CATALYST ACTIVITY; HYDROGENATION; KETONES; RUTHENIUM COMPOUNDS;

EID: 42449143424     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om700940m     Document Type: Article
Times cited : (47)

References (65)
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    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keit
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
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    • A related H-bond has been suggested to play a role in enantioselective hydrogenation of acetylthiophene. See: Cao, P, Zhang, X. M. J. Org. Chem. 1999, 64, 2127-2129
    • A related H-bond has been suggested to play a role in enantioselective hydrogenation of acetylthiophene. See: Cao, P.; Zhang, X. M. J. Org. Chem. 1999, 64, 2127-2129.
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    • Evidence for a related mechanism is also provided in: Sandoval, C. A.; Ohkuma, T.; Utsume, N.; Tsutsumi, K.; Murata, K.; Noyori, R. Chem. As. J. 2006, 102.
    • Evidence for a related mechanism is also provided in: Sandoval, C. A.; Ohkuma, T.; Utsume, N.; Tsutsumi, K.; Murata, K.; Noyori, R. Chem. As. J. 2006, 102.
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    • See for example
    • See for example: Grimme, S. J. Comput. Chem. 2004, 25, 1463-1473.
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    • Grimme, S.1
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    • It is possible to compute the difference in the free energies of activation for the two TSs at the B3LYP/6-31G* level, using expressions for the partition functions based on the rigid rotor/harmonic oscillator approximation, and this yields a difference of 2.03 kcal/mol. This value is not necessarily a closer approximation to the true difference in free energies of activation than is the difference in the energies of activation, given the errors involved in applying gas-phase rigid rotor/harmonic oscillator expressions to the reaction in solution, but it is satisfying to note ΔΔG‡ is similar to ΔΔE ‡
    • ‡.
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    • In a recent computational study of enantioselectivity in hydrogenation of acetophenone by (SXylBINAP)RuH2(S,S-dpen),45 a different explanation has been given for the selectivity. The hydrogen transfer TSs located in this study are similar to those obtained here. The authors have also located weak hydrogen-bonded complexes between the dihydride catalyst and the ketone, similar in geometry to the intermediate B shown in Figure 2. As discussed above, such minima are likely to disappear in the presence of solvent and when taking entropic factors into account, so should not play an important role in the mechanism. However, in the case of the ax-out approach only, the authors located a second stable intermediate in which me ketone has moved closer to the transferring hydride and suggest that the presence of this stable species helps to explain the selectivity. No such minimum has been found in the present case, perhaps because the less bulky BINAP ligand was modeled ins
    • 45 a different explanation has been given for the selectivity. The hydrogen transfer TSs located in this study are similar to those obtained here. The authors have also located weak hydrogen-bonded complexes between the dihydride catalyst and the ketone, similar in geometry to the intermediate B shown in Figure 2. As discussed above, such minima are likely to disappear in the presence of solvent and when taking entropic factors into account, so should not play an important role in the mechanism. However, in the case of the ax-out approach only, the authors located a second stable intermediate in which me ketone has moved closer to the transferring hydride and suggest that the presence of this stable species helps to explain the selectivity. No such minimum has been found in the present case, perhaps because the less bulky BINAP ligand was modeled instead of XylBINAP. Since BINAP gives a similar pattern of stereoselectivity to XylBINAP, it is unlikely that any major effect is present with the latter ligand that is absent with BINAP. The appearance of the energy plot in ref 41 (Figure 2) suggests a conformational change, perhaps in the bulky xylyl sidechains, upon approach of the ketone. Such a change is unlikely to be rate-determining since it can also occur before the ketone binds.
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    • In fact, the prediction in our earlier work (ref 16) that hydrogen splitting was turnover limiting was made before experimental evidence for this became available
    • In fact, the prediction in our earlier work (ref 16) that hydrogen splitting was turnover limiting was made before experimental evidence for this became available.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.