Isomerization of aldehydes catalyzed by rhodium(I) olefin complexes

Angewandte Chemie - International Edition

Volumn 38, Issue 23, 1999, Pages 3533-3537

  Lenges, Christian P ^a   Brookhart, Maurice ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

Aldehydes; C H activation; Hydroformylations; Isomerizations; Rhodium

Indexed keywords

ALDEHYDE; ALKENE; RHODIUM COMPLEX;

ANALYTIC METHOD; ARTICLE; CATALYSIS; CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL STRUCTURE; ISOMERISM; MOLECULAR INTERACTION;

EID: 0033521183     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19991203)38:23<3533::AID-ANIE3533>3.0.CO;2-E     Document Type: Article

References (35)

1. O. Roelen (Ruhrchemie A. G.). German Patent 849548, 1938.
2. G. Wilkinson, J. A. Osborn, D. J. Evans, J. Chem. Soc. A 1968, 3133.
3. a) G. W. Parshall, S. D. Ittel, Homogeneous Catalysis: The Application and Chemistry of Catalysis by Soluble Transition Metal Complexes 2nd ed., Wiley, New York. 1992;
4. b) M. Beller, B. Cornils, C. D. Frohning, C. W. Kohlpaintner, J. Mol. Catal. A 1995, 104(1), 17-85.
5. I. Tkatchenko in Comprehensive Organometallic Chemistry, Vol. 8 (Eds.: G. Wilkinson, F. G. A. Stone, E. W. Abel), Pergamon, Oxford, 1982, pp. 101.
6. R. L. Pruett, Ann. N. Y. Acad. Sci. 1977, 195, 239.
7. L. M. Petrovich, C. P. Casey, J. Am. Chem. Soc. 1995, 117, 6007.
8. a) L. A. Van der Veen, P. C. J. Kamer, P. W. N. M. Van Leeuwen, Angew. Chem. 1999, 111, 349-351; Angew. Chem. Int. Ed. 1999, 38, 336;
9. a) L. A. Van der Veen, P. C. J. Kamer, P. W. N. M. Van Leeuwen, Angew. Chem. 1999, 111, 349-351; Angew. Chem. Int. Ed. 1999, 38, 336;
10. b) B. Breit, Eur. J. Org. Chem. 1998, 1123-1134;
11. c) K. Nozaki, H. Takaya, T. Hiyama, Top. Catal. 1998, 4, 175.
12. C. P. Casey, E. L. Paulsen, E. W. Beuttenmueller, B. R. Proft, B. A. Matter, D. R. Powell, J. Am. Chem. Soc. 1999, 121, 63.
13. The C-H bond activation of aldehydes has been described and was applied until recently predominantly in aldehyde decarbonylation reactions to generate a metal-CO complex and the parent alkane. H. M. Colquhoun, D. J. Thomson, M. V. Twigg, Carbonylation: Direct Synthesis of Carbonyl Compounds, Plenum, New York, 1991.
14. J. Tsuji, K. Ohno, Synthesis 1969, 157.
15. J. Tsuji, K. Ohno, J. Am. Chem. Soc. 1968, 90, 99.
16. M. Brookhart, C. P. Lenges, P. S. White, J. Am. Chem. Soc. 1998, 120, 6965.
17. C. P. Lenges, M. Brookhart, J. Am. Chem. Soc. 1997, 119, 3165.
18. C.-H. Jun, J.-B. Hong, D.-Y. Lee, Synlett 1999, 1.
19. B. Bosnich, Acc. Chem. Res. 1998, 31, 667.
20. In some Ru-catalyzed hydroacylation reactions the transfer formylation of benzaldehyde and cyclohexene to benzene and cyclohexane-carbaldehyde has been observed. T. Kondo, M. Akazome, Y. Tsuij, Y. Watanabe, J. Org. Chem. 1990, 55, 1286.
21. 2] with iPrMgBr. J. Müller, H.-O. Stühler, W. Goll, Chem. Ber. 1975, 108, 1074.
22. 5Rh] complex has been reported: L. P. Seiwell, Inorg. Chem. 1976, 15, 2560.
23. The formation of isomers was also observed in analogous rhodium methylacrylate complexes. E. Hauptman, S. Sabo-Etienne, P. S. White, M. Brookhart, J. M. Garner, P. J. Fagan, J. C. Calabrese, J. Am. Chem. Soc. 1994, 116, 8038.
24. 1) was generated in a reaction with propionaldehyde, but was too unstable for isolation. P. M. Maitlis, G. J. Sunley, J. M. Kisenyi, M. Gomez, J. Organomet. Chem. 1985, 296, 197.
25. 6]benzene at 50°C yields 4 (≈85%) and other unassigned organometallic complexes in addition to n-butanal, propene, and propane.
26. A. Nutton, P. M. Maitlis, J. Organomet. Chem. 1979, 166, C21.
27. a) Catalytic hydroacylation of aromatic aldehydes is observed using complexes of type 2 at 100°C with 5 turnovers per hour; alkyl aldehydes are not converted under these conditions: C. P. Lenges, M. Brookhart, unpublished results;
28. b) the presence of acid impurities in the reaction mixture can terminate catalysis and is more significant in reactions with reduced catalyst loading.
29. a) Based on the heats of formation of n- and iso-butyraldehydes and calculated entropies of formation, the thermodynamic ratio of these aldehydes should be about 1:1. See K. B. Wiberg, L. S. Crocker, K. M. Morgan, J. Am. Chem. Soc. 1991, 113, 3447;
30. b) during catalytic hydroacylation reactions using cobalt analogues only the formation of the Co-n-alkyl intermediates was observed in the reaction of the isomeric butanals, which is in line with the results observed here for 3 versus 3′. The formation of the branched alkyl intermediate was suggested by labeling studies and the formation of isomeric product mixtures but not directly observed; see reference [12].
31. In addition, propene, and the isomeric butanals are observed in the reaction mixture.
32. 2 was prepared as the precursor following the literature procedure. P. G. Gassman, J. W. Mickelson, J. R. Sowa, Jr., J. Am. Chem. Soc. 1992, 114, 6942. Using this dimer, complex 5 was prepared in a zinc reduction using an analogous procedure as described for 2. Experimental details will be reported in a separate manuscript.
33. [1] intermediates, which would result in increased activity.
34. The formation of an intermediate with the same characteristics as 7 was also observed in a reaction of l-phenylpropanal with 6. At this point an alternative structure for 7 can not be excluded (for example, the branched isomer as in 3′).
35. C. P. Lenges, P. S. White, M. Brookhart, J. Am. Chem. Soc. 1999, 121, 4385.