Palladium-Catalyzed Isomerization and Hydroformylation of Olefins
FULL PAPER
and heated to 1008C. The reaction was carried out for 16 h; then, the
pressure was released and isooctane (internal standard) was added to the
solution. The yield was measured by GC. Product characterization was
done by comparison with authentic samples and HR-MS.
[11] a) R. Jackstell, H. Klein, M. Beller, K.-D. Wiese, D. Rottger, Eur. J.
Beller, H. Fischer, W. A. Herrmann, C. Broßmer, Angew. Chem.
d) W. A. Herrmann, C. Broßmer, K. ꢇfele, T. Priermeier, M. Beller,
mann, A. Zapf, D. Strꢁbing, S. Hꢁbner, J. Almena, T. Riermeier, P.
Groß, M. Sarich, W.-R. Krahnert, K. Rossen, M. Beller, Angew.
e) A. Tewari, M. Hein, A. Zapf, M. Beller, Synthesis 2004, 935; f) H.
Neumann, A. Brennfꢁhrer, P. Groß, T. Riermeier, J. Almena, M.
Neumann, S. Klaus, P. Groß, T. Riermeier, J. Almena, M. Beller,
[14] a) R. Jackstell, S. Harkal, H. Jiao, A. Spannenberg, C. Borgmann, D.
Rçttger, F. Nierlich, M. Elliot, S. Niven, K. Cavell, O. Navarro, M. S.
Harkal, R. Jackstell, F. Nierlich, D. Ortmann, M. Beller, Org. Lett.
2005, 7, 541; c) A. Frisch, N. Shaikh, A. Zapf, M. Beller, O. Briel, B.
3901; g) R. Jackstell, M. Gomez Andreu, A. Frisch, H. Klein, K. Sel-
vakumar, A. Zapf, A. Spannenberg, D. Rçttger, O. Briel, R. Karch,
[15] a) A. Zapf, R. Jackstell, F. Rataboul, T. Riermeier, A. Monsees, C.
2004, 38; b) F. Rataboul, A. Zapf, R. Jackstell, S. Harkal, T. Rierme-
2983; c) S. Harkal, K. Kumar, D. Michalik, A. Zapf, R. Jackstell, F.
2005, 46, 3237; d) M. Beller, A. Zapf, A. Monsees, T. H. Riermeier,
Chim. Oggi. 2004, 22, 16; e) C. Torborg, A. Zapf, M. Beller, Chem-
Acknowledgements
We gratefully acknowledge Evonik Oxeno, the state Mecklenburg-Vor-
pommern, the Bundesministerium fꢁr Bildung und Forschung (BMBF) ,
and the DFG (Leibniz-Prize) for financial support.
[1] a) Aqueous-Phase Organometallic Catalysis (Eds.: B. Cornils, W. A.
Herrmann), VCH, Weinheim: 1998; b) Rhodium-catalyzed Hydro-
formylation (Eds.: P. W. N. M. van Leeuwen, C. Claver), Kluwer
Academic, Dordrecht, 2000.
[3] a) C. Rein, P. Demel, R. A. Outten, T. Netscher, B. Breit, Angew.
C. Bassarello, G. Bifulco, L. Gomez-Paloma, A. Mann, M. Marche-
tti, A. Schoenfelder, M. Taddei, Synlett 2005, 10, 1581; d) E. Cesar-
Breit, Angew. Chem. 2008, 120, 317; Angew. Chem. Int. Ed. 2008, 47,
311; b) L. Leclercq, I. Suisse F. Agbossou-Niedercorn, Chem.
Dieguez, O. Pamies, S. Castillon, Top. Organomet. Chem. 2006, 35;
e) M. Kuil, P. E. Goudriaan, P. W. N. M. van Leeuwen, J. N. H. Reek,
Chem. 2006, 98, 1324; h) A. T. Axtell, C. J. Cobley, J. Klosin, G. T.
Ruiz , C. Claver, Tetrahedron: Asymmetry 2001, 12, 2827; j) M. Diꢅ-
guez, O. Pꢆmies, G. Net, A. Ruiz, C. Claver, Tetrahedron: Asymme-
try 2001, 12, 651.
[5] a) A. Kaizik, K.-D. Wiese, D. Maschmeyer, D. Hess, W. Bueschken,
F. Nierlich (Evonik), PCT Int. Appl., WO2008006633, 2008; b) R. V.
Chaudhari, Curr. Opin. Clin. Nutr. Metab. Care Curr. Opin. Drug
Discovery Dev. 2008, 11, 820; c) E. Drent, R. J. Van Ginkel, W.
Willem (Shell), Int. Appl., WO2004028689, 2004; d) B. Cornils, J.
[6] a) G. Protzmann, K.-D. Wiese, Erdçl Erdgas Kohle 2001, 117, 235;
b) C. W. Kohlpaintner, R. W. Fischer, B. Cornils, Appl. Catal. 2001,
221, 219; c) J. Herwig, R. Fischer in Rhodium Catalyzed Hydrofor-
mylation (Eds.: P. W. N. M. van Leeuwen, C. Claver), Kluwer Aca-
demic, Dordrecht, 2000, p. 189.
[16] a) T. Schulz, C. Torborg, B. Schꢂffner, J. Huang, A. Zapf, R. Kadyr-
[17] In a 250 mL schlenk flask with reflux condenser under argon 1-
(naphthalen-1-yl)-1H-pyrrole (5 g, 25.9 mmol) was dissolved in Et2O
(100 mL), and TMEDA (6.04 g, 7.8 mL, 52 mmol) was added at
room temperature. After addition of 1.6n nBuLi (32.5 mL,
52 mmol) the solution was stirred for 5 h at room temperature.
Then, dicyclohexylchlorophosphine (12.06 g, 11.4 mL, 52 mmol) was
added. After stirring for 1 h at room temperature, degassed water
(50 mL) was introduced. The organic phase was washed degassed
water (3ꢀ20 mL) and the solvents were removed in vacuum. The
residue was recrystallized from MeOH (200 mL). The resulting
white solid was filtered to give 2-(dicyclohexylphosphino)-1-(2-(dicy-
clohexylphosphino)naphthalen-1-yl)-1H-pyrrole (13.5 g, 90% yield).
[7] a) C. W. Kohlpaintner, R. W. Fischer, B. Cornils, Appl. Catal. 2001,
Bohnen, B. Cornils, Adv. Synth. Catal. 2002, 344, 1; d) W. A. Herr-
[8] a) H. Fu, M. Li, J. Chen, R. Zhang, W. Jiang, M. Yuan, H. Chen, X.
nares, A. Bruss, R. Santos, E. Lujano, R. A. Sanchez-Delgado, J.
31P NMR (121.5 MHz, CDCl3): d=À14.4, À26.6 ppm (dd, JPP
=
[9] F. P. Pruchnik, Organometallic Chemistry of Transition Elements,
Plenum Press, New York, 1990, p. 691.
14.8 Hz); 1H NMR (300 MHz, CDCl3): d=8.27 (d, J=7 Hz, 1H),
8.24 (d, J=8 Hz, 1H), 8.04 (dd J=8.5 Hz, J=1.4 Hz, 1H), 7.84 (td,
Chem. Eur. J. 2009, 15, 6383 – 6388
ꢃ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6387