Mechanistic study on hydrogenation of electron-rich substrates with electron-deficient Rh-BINAP catalyst

doi:10.7523/j.issn.2095-6134.2012.4.021

Abstract

Abstract: Four electron-rich α-acetamidocinnamic acid derivatives were prepared and used as substrates in the asymmetric hydrogenation catalyzed by electron-deficient Rh-3,5-CF₃-(R)-BINAP. Influence of the electronic properties of substituted groups in the substrates and their steric hindrance on the enantioselectivity of the product were discussed.

Key words: electron-rich substrates, electron-deficient Rh-BINAP catalyst, asymmetric hydrogenation, mechanism

CLC Number:

HUANG Bi-Yu, WU Hai-Chen, YANG Jing-Kui. Mechanistic study on hydrogenation of electron-rich substrates with electron-deficient Rh-BINAP catalyst[J]. , 2012, 29(4): 571-575.

References

[1] Knowles W S, Sabacky M. Catalytic asymmetric hydrogenationemploying a soluble, optically active, rhodium complex[J]. Chem Commun, 1968, 17(22): 1445-1446.
[2] Horner L, Siegel H, Buthe H. Asymmetric catalytic hydrogenationwith an optically active phosphine rhodium complex in homogeneoussolution[J]. Angew Chem Int Ed Engl, 1968, 7: 942-946.
[3] Tang W J, Zhang X M. New chiral phosphorus ligands for enantioselective hydrogenation[J]. Chem Rev, 2003, 103(8): 3029-3070.
[4] Halpern J. Mechanistic aspects of homogeneous catalytic hydrogenation and related processes [J]. Inorg Chim Acta, 1981, 50: 11-19.
[5] Halpern J, Riley D P, Chan A S C, et al. Novel coordination chemistry and catalytic properties of cationic 1,2-bis(diphenylphosphino)ethanerhodium(I) complexes[J]. J Am Chem Soc, 1977, 99(24): 8055-8057.
[6] Chan A S C, Pluth J J, Halpern J. Intermediates in homogeneous catalytic hydrogenation. The crystal and molecular structure of the methyl(Z)-α-acetamodicinnamate adduct of 1,2-bis(diphenylphosphino)ethanerhodium(I) [J]. Inorg Chim Acta, 1979, 37: L477-L479.
[7] Chan A S C, Halpern J, Pluth J J. Identification of the enantioselective step in the asymmetric catalytic hydrogenation of a prochiral olefin[J]. J Am Chem Soc, 1980, 102(18): 5952-5954.
[8] Brown J M, Chaloner P A. The mechanism of asymmetric homogeneous hydrogenation. Rhodium(I) complexes of dehydroamino acids containing asymmetric ligands related to bis(1,2-diphenylphosphino)ethane[J]. J Am Chem Soc, 1980, 102(9): 3040-3048.
[9] Brown J M, Chaloner P A, Kent A G, et al. The mechanism of asymmetric homogeneous hydrogenation. Solvent complexes and dihydrides from rhodium diphosphine precursors [J]. J Organomet Chem, 1981, 216(2): 263-276.
[10] Brown J M, Chaloner P A, Morris G A. Identification of a further transient species relating to rhodium-complex catalysed asymmetric hydrogenation[J]. J Chem Soc Chem Commun, 1983: 664-666.
[11] Birtwistle D H, Brown J M, Herbert R H, et al. Conformational analysis in the directed hydrogenation of homoallylic alcohols[J]. J Chem Soc Chem Commun, 1989: 194-196.
[12] Ando D, Bevan C, Brown J M, et al. Contrasting pathways for the directed homogeneous hydrogenation of vinyl sulfoxides and vinyl sulfones[J]. J Chem Soc Chem Commun, 1992: 592-594.
[13] Gridnev I D, Higashi N, Asakura K, et al. Mechanism of asymmetric hydrogenation catalyzed by a rhodium complex of (S,S)-1,2-Bis(tert-butylmethylphosphino)ethane. Dihydride mechanism of asymmetric hydrogenation[J]. J Am Chem Soc, 2000, 122(30): 7183-7194.
[14] Gridnev I D, Yasutake M, Higashi N, et al. Asymmetric hydrogenation of enamides with Rh-BisP^* and Rh-MiniPHOS catalysts. scope, limitations, and mechanism[J]. J Am Chem Soc, 2001, 123(22): 5268-5276.
[15] Halpern J. Mechanism and stereoselectivity of asymmetric hydrogenation[J]. Science, 1982, 217(4558): 401-407.
[16] Knowles W S. Asymmetric hydrogenation[J]. Acc Chem Res, 1983, 16(3): 106-112.
[17] Yu J Q, Specer J B. First evidence that the mechanism of catalytic hydrogenation with homogeneous palladium and rhodium catalysts is strongly influenced by substrate polarity[J]. J Am Chem Soc, 1997, 119(22): 5257-5258.
[18] Wu H C, Hamid S A, Yu J Q, et al. Possible origin of electronic effects in Rh(I)-catalyzed enantioselective hydrogenation[J]. J Am Chem Soc, 2009, 131(28): 9604-9605.
[19] Cutolo M, Fiandanese V, Naso F, et al. Synthesis of dehydrophenylalanine derivatives by palladium catalyzed arylation of 2-acetamidoacrylic acid[J]. Tetrahedron Lett, 1983, 24(42): 4603-4606.