Counterintuitive kinetics in Tsuji-Trost allylation: Ion-pair partitioning and implications for asymmetric catalysis

Journal of the American Chemical Society

Volumn 130, Issue 44, 2008, Pages 14471-14473

  Evans, Louise A ^a   Fey, Natalie ^a   Harvey, Jeremy N ^a   Hose, David ^b   Lloyd Jones, Guy C ^a   Murray, Paul ^b   Orpen, A Guy ^a   Osborne, Robert ^b   Owen Smith, Gareth J J ^a   Purdie, Mark ^b  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

^b ASTRAZENECA   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLATION; ARTICLE; ASYMMETRIC CATALYSIS; CATALYSIS; CATALYST; ENANTIOSELECTIVITY; PARTITION CHROMATOGRAPHY; STOICHIOMETRY;

ALLYL COMPOUNDS; CATALYSIS; IONS; KINETICS; NAPHTHALENES; PALLADIUM; PHOSPHINES;

EID: 55549096037     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja806278e     Document Type: Article

References (46)

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3. (a) Atkins, K. E.; Walker, W. E.; Manyik, R. M. Tetrahedron Lett. 1970, 11, 3821.
4. (b) See reference 1 cited in ref 3a for an extensive list of reviews.
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7. (c) Pfaltz, A.; Lautens, M. Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, Germany, 1999; pp 833-886.
8. Studies reporting on the kinetics of catalytic reaction: (a) Mackenzie, P. B.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2046.
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11. (d) Gais, H.-J.; Jagusch, T.; Spalthoff, N.; Gerhards, F.; Frank, M.; Raabe, G. Chem. - Eur. J. 2003, 9, 4202.
12. Studies reporting on the kinetics of stoichiometric amination of π-allyl Pd complexes: (e) Vitagliano, A.; Åkermark, B. J. Organomet. Chem. 1988, 349, C22.
13. (f) Kuhne, O.; Mayr, H. Angew Chem. Int. Ed. 1999, 38, 343.
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15. Studies reporting on the kinetics of stoichiometric oxidative addition of allyl esters to generate π-allyl Pd complexes: (h) Amatore, C.; Jutand, A.; Meyer, G.; Mottier, L. Chem. - Eur. J. 1999, 5, 466.
16. (i) Amatore, C.; Gamez, S.; Jutand, A. Chem. - Eur. J. 2001, 7, 1273.
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19. (l) Amatore, C.; Bahsoun, A. A.; Jutand, A.; Mensah, L.; Meyer, G.; Ricard, L. Organometallics 2005, 24, 1569.
20. For a similar (but qualitative) trend, ascribed to an "ionic liquid effect", see: (a) Ross, J.; Chen, W.; Xu, L.; Xiao, J. Organometallics 2001, 20, 138.
21. For a related acetate sequestering effect through H-bonding, that suppresses rate, see: (b) Ross, J.; Xiao, J. Chem. - Eur. J. 2003, 9, 4900.
22. Brookhart, M.; Grant, B.; Volpe, A. F. Organometallics 1992, 11, 3920.
23. (a) Winstein, S.; Klinedinst, P. E.; Robinson, G. C. J. Am. Chem. Soc. 1954, 76, 2597.
24. (b) At present it is unclear whemer the approximately linear plots in Figure 1 are the early phases of a special salt effect (which should progressively inflect to a normal salt effect) or the linear portion of a, rather powerful, normal salt effect. Scheme 3 supports the former.
25. Crotyl acetate behaved analogously. See Supporting Information.
26. Nu), see reference 4g.
27. Ligand association/dissociation equilibria are not implicated: the bidentate dppf ligands (entries 11-13) give identical trends. Addition of 1 equiv ligand v (entry 5) resulted in severe attenuation of turnover rate.
28. Akermark, B.; Hansson, S.; Zetterberg, K.; Krakenberger, B.; Vitagliano, A. Organometallics 1984, 3, 679.
29. 19F PGSE diffusion) that BAr′F engages in "very modest but not zero ion pairing", see: (a) Nama, D.; Butti, P.; Pregosin, P. S. Organometallics 2007, 26, 4942.
30. (b) Pregosin, P. S. Prog. Nucl. Magn. Reson. Spectrosc. 2006, 49, 261.
31. tot][2] may only hold for low [NaBAr′F] concentrations. See also ref 7b.
32. 3P, see: Yamamoto, T.; Saito, O.; Yamamoto, A. J. Am. Chem. Soc., 1981, 103, 5600.
33. 2][BAr′F] are K = 0.43 ± 0.11 (i), and K = 193 ± 147 (v), see Supporting Information.
34. Reactions were substantially slower than in THF, see Supporting Information, and proceeded with very approximately pseudo-zero-order kinetics, as might be expected from a steady-state concentration of [2].
35. For other examples of pseudo-zero-order competitive networks see: (a) Ferretti, A. C.; Mathew, J. S.; Ashworth, I.; Purdy, M.; Brennan, C.; Blackmond, D. G. Adv. Synth. Catal. 2008, 350, 1007.
36. (b) Blackmond, D. G.; Hodnett, N. S.; Lloyd-Jones, G. C. J. Am. Chem. Soc. 2006, 128, 7450.
37. (c) Dominguez, B.; Hodnett, N. S.; Lloyd-Jones, G. C. Angew. Chem., Int. Ed. 2001, 40, 4289.
38. 2 for limiting 1a. Using more electron rich ligands, the selectivity for 2 could be approximately doubled by addition of 3.0 mM [NaBAr′F], see Supporting Information.
39. 1b (0.15 → 0.50) with [4(BINAP)][OTf].
40. The generation of a less-intimate ion-pair (see ref 12) may also modulate "memory effects". For leading references: (a) Trost, B. M.; Bunt, R. C. J. Am. Chem. Soc. 1996, 118, 235.
41. (b) Lloyd-Jones, G. C.; Stephen, S. C.; Fairlamb, I. J. S.; Martorell, A.; Dominguez, B.; Tomlin, P. M.; Murray, M.; Fernandez, J. M.; Jeffery, J. C.; Riis-Johannessen, T.; Guerziz, T. Pure Appl. Chem. 2004, 76, 589.
42. (c) Svensen, N.; Fristrup, P.; Tanner, D.; Norrby, P.-O. Adv. Synth. Catal. 2007, 349, 2631.
43. Detrimental effects of halide on the selectivity of asymmetric allylation are known, see for example: Clark, T. P.; Landis, C. R. J. Am. Chem. Soc., 2003, 125, 11792.
44. Previously reported to proceed in 30% ee with X = Cl: Yamaguchi, M.; Shima, T.; Yamagishi, T. Tetrahedron: Asymmetry 1991, 2, 663.
45. Nu leading to a Pd-allyl species as resting state, see reference 4a.
46. BAr′F, or analogous "non-interactive" (ref 12) anions are often employed in systems propagating via contiguous cationic catalytic intermediates. The results herein show that BAr′F can also be applied to catalytic cycles with neutral and cationic intermediates.