Anti-Markovnikov Hydrofunctionalization of Olefins Mediated by Rhodium-Porphyrin Complexes

Angewandte Chemie - International Edition

Volumn 43, Issue 5, 2004, Pages 588-590

  Sanford, Melanie S ^a   Groves, John T ^a  

^a PRINCETON UNIVERSITY   (United States)

Author keywords

Alkenes; Hydroamination; Porphyrinoids; Reductive elimination; Rhodium

Indexed keywords

AROMATIC COMPOUNDS; CATALYST ACTIVITY; CATALYST SELECTIVITY; CHEMICAL BONDS; COMPLEXATION; PORPHYRINS; REACTION KINETICS; REDUCTION; RHODIUM COMPOUNDS; SYNTHESIS (CHEMICAL);

HETEROCYCLIC COMPOUNDS; HYDROFUNCTIONALIZATION;

OLEFINS;

ALKENE; FUNCTIONAL GROUP; PORPHYRIN; RHODIUM COMPLEX; TETRAPHENYLPORPHYRIN;

ADDITION REACTION; AMINATION; ARTICLE; CATALYSIS; CHEMICAL BOND; CYCLIZATION; ELIMINATION REACTION; PROTON NUCLEAR MAGNETIC RESONANCE; REDUCTION;

ALKENES; CATALYSIS; HYDROGEN BONDING; MOLECULAR STRUCTURE; PORPHYRINS; RHODIUM;

EID: 1042288502     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351941     Document Type: Article

References (29)

1. B. M. Trost, Science 1991, 254, 1471-1477.
2. J. Haggin, Chem. Eng. News 1993, 71(22), 23.
3. a) C. M. Jensen, W. C. Trogler, Science 1986, 233, 1069-1071;
4. b) D. Ramprasad, H. J. Yue, J. A. Marsella, Inorg. Chem. 1988, 27, 3151-3155.
5. a) M. Utsunomiya, R. Kuwano, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2003, 125, 5608-5609;
6. b) M. Beller, C. Breindl, M. Eichberger, C. G. Hartung, J. Seayad, O. R. Thiel, A. Tillack, H. Trauthwein, Synlett, 2002, 10, 1579-1594;
7. c) M. Beller, O. R. Thiel, H. Trauthwein, C. G. Hartung, Chem. Eur. J. 2000, 6, 2513-2522;
8. d) M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, T. E. Muller, Eur. J. Inorg. Chem. 1999, 1121-1132;
9. e) M. Beller, H. Trauthwein, M. Eichberger, C. Breindl, J. Herwig, T. E. Muller, O. R. Thiel, Chem. Eur. J. 1999, 5, 1306-1319.
10. For an alternative approach, see: A. Seayad, M. Ahmed, H. Klein, R. Jackstell, T. Gross, M. Beller, Science 2002, 297, 1676-1678.
11. R. H. Crabtree, The Organometallic Chemistry of the Transition Metals, 2nd ed., Wiley, New York, 2001, chap. 7.
12. For recent examples of direct carbon-heteroatom bond-forming reductive elimination under mild conditions, see: a) B. S. Williams, K. I. Goldberg, J. Am. Chem. Soc. 2001, 123, 2576-2587;
13. b) J. F. Hartwig, Acc. Chem. Res. 1998, 31, 852-860;
14. c) S. S. Stahl, J. A. Labinger, J. E. Bercaw, Angew. Chem. 1998, 110, 2298-2311; Angew. Chem. Int. Ed. 1998, 37, 2181-2192.
15. c) S. S. Stahl, J. A. Labinger, J. E. Bercaw, Angew. Chem. 1998, 110, 2298-2311; Angew. Chem. Int. Ed. 1998, 37, 2181-2192.
16. Reductive elimination induced by oxidation is more common; for a recent example, see: a) B. L. Lin, C. R. Clough, G. L. Hillhouse, J. Am. Chem. Soc. 2002, 124, 2890-2891.
17. II· intermediates) has been studied, but its scope and functional-group tolerance have not been reported. a) X. F. Fu, L. Basickes, B. B. Wayland, Chem. Commun. 2003, 520-521;
18. b) K. W. Mak, F. Xue, T. C. W. Mak, K. S. Chan, J. Chem. Soc. Dalton Trans. 1999, 3333-3334;
19. c) D. J. Anderson, R. Eisenberg, Organometallics 1996, 15, 1697-1706;
20. d) R.S. Paonessa, N. C. Thomas, J. Halpern, J. Am. Chem. Soc. 1985, 107, 4333-4334;
21. 1H-Rh coupling and on upfield shifts of the alkyl resonances.[9] The linear product was formed in situ in > 90% yield, whereas the branched isomer was not detected; thus, the lower limit of regioselectivity corresponds to ∼97%.
22. a) K. J. Delrossi, X. X. Xhang, B. B. Wayland, J. Organomet. Chem. 1995, 504, 47-56;
23. b) B. B. Wayland, S. J. Ba, A. E. Sherry J. Am. Chem. Soc. 1991, 113, 5305-5311.
24. a) A. P. Nelson, S. G. Dimagno, J. Am. Chem. Soc. 2000, 122, 8569-8570;
25. b) J. P. Collman, J. I. Brauman, A. M. Madonik, Organometallics 1986, 5, 215-218.
26. H.-Z. Han, Ph.D. Thesis, Princeton University, 1992.
27. The origin of this effect is currently under investigation.
28. K. A. Cooper, M. L. Dhar, E. D. Hughes, C. K. Ingold, B. J. MacNulty, L. I. Woolf, J. Chem. Soc. 1948, 2043-2049.
29. 6]DMSO produced a complex mixture of (TPP)Rh products owing to the apparent instability of (TPP)Rh-H in this medium.