COMMUNICATIONS
were carried out on an AMX600 NMR spectrometer (Bruker, Karlsruhe,
Germany) equipped a 5 mm triple-resonance probehead with z-gradients.
Edman degradation was performed on a Hewlett ± Packard 241 protein
sequencer equipped with a biphasic column detector (Hewlett ± Packard,
Waldbronn, Germany). For amino acid analysis with GC-MS (HP 5973/
HP 6890, Agilent Technologies, Waldbronn, Germany), the peptides were
hydrolyzed under vacuum (6n HCl containing 5% phenol, 1108C, 24 h)
and derivatized with methanol/HCl (2n, 1108C, 15 min), trifluoroacetic
anhydride (1108C, 10 min), and then BSTFA/HMDS/pyridine (4:1:4, 808C,
30 min; BSTFA N,O-bis(trimethylsilyl) trifluoroacetamide, HMDS
1,1,1,3,3,3-hexamethyldisilazane), and analyzed by GC-MS on fused silica
capillaries (25 m  0.25 mm) coated with either l-Chirasil-Val or Lip-
odex E (30%) in PS255 (film thickness df 0.13 mm). For sugar analysis,
SP-1294 was subjected to methanolysis (HCl (0.65n) in methanol/methyl
acetate (4:1), 708C, 16 h). The trimethylsilyl derivatives were prepared by
using BSTFA/pyridine (1:1, 808C, 30 min), and analyzed by GC-MS on an
HP 1-MS fused silica capillary (30 m  0.25 mm; df 0.25 mm, Agilent
Technologies).
New Phosphorus Ligands for the Rhodium-
Catalyzed Isomerization/Hydroformylation of
Internal Octenes
Detlef Selent,* Dieter Hess, Klaus-Diether Wiese,
Dirk Röttger, Christine Kunze, and Armin Börner*
The synthesis of placticizers is closely related to the
n-regioselective hydroformylation of olefins. World-wide,
propene is an important feed stock in the rhodium-catalyzed
synthesis of n-butanal. The use of higher internal olefins, for
example di-n-butene from fraction II of the refining process,
offers a very interesting and financially attractive alternative
that is also used industrially. In these processes the use of
unmodified cobalt catalysts and cobalt ± phosphane com-
plexes is dominant. At 80 ± 350 bar and 160 ± 1908C regiose-
lectivities of around 50% with regard to the desired terminal
hydroformylation product are achieved, this can be increased
to over 80% by modifying the catalyst with a suitable
phosphine ligand.[1]
Received: December 27, 2000 [Z16325]
[1] M. K. McCormick, W. M. Stark, G. E. Pittenger, R. C. Pittenger,
G. M. McGuire, Antibiot. Annu. 1955/1956, 606 ± 611. Structure
elucidation: a) G. M. Sheldrick, P. G. Jones, O. Kennard, D. H.
Williams, G. A. Smith, Nature 1978, 271, 223 ± 225; b) P. J. Loll, A. E.
Bevivino, B. D. Korty, P. H. Axelson, J. Am. Chem. Soc. 1997, 119,
1516 ± 1522; c) C. M. Harris, H. Kopecka, T. M. Harris, J. Am. Chem.
Soc. 1983, 105, 6915 ± 6922; d) S. G. Grdadolnik, P. Pristovsek, D. F.
Mierke, J. Med. Chem. 1998, 41, 2090 ± 2099.
The development of a catalyst that delivers high activities
and selectivities under mild conditions is not only of industrial
importance, Scheme 1 illuminates the scientific problems with
[2] R. C. Yao, L. W. Crandall in Glycopeptide Antibiotics (Ed.: R.
Nagarajan), 1st ed., Marcel Dekker, New York, 1994, pp. 1 ± 21.
[3] a) H. R. Perkins, Biochem. J. 1969, 111, 195 ± 205; b) J. R. Kalman,
D. H. Williams, J. Am. Chem. Soc. 1980, 102, 906 ± 912.
b
a
c
[4] a) D. H. Williams, B. Bardsley, Angew. Chem. 1999, 111, 1264 ± 1286;
Angew. Chem. Int. Ed. 1999, 38, 1172 ± 1193; b) K. C. Nicolaou,
C. N. C. Boddy, S. Bräse, N. Winssinger, Angew. Chem. 1999, 111,
2230 ± 2287; Angew. Chem. Int. Ed. 1999, 38, 2096 ± 2152.
[5] A. M. A. van Wageningen, P. N. Kirkpatrick, D. H. Williams, B. R.
Harris, J. K. Kershaw, N. J. Lennard, M. Jones, S. J. M. Jones, P. J.
Solenberg, Chem. Biol. 1998, 5, 155 ± 162.
OHC
d
+ CO/ H2
Kat.: [Rh]
CHO
Scheme 1. Isomerization and hydroformylation of (Z)/(E)-4-octene.
[6] S. Chatterjee, E. K. S. Vijayakumar, S. R. Nadkarni, M. V. Patel, J.
Blumbach, B. N. Ganguli, H.-W. Fehlhaber, H. Kogler, L. Vertesy, J.
Org. Chem. 1994, 59, 3480 ± 3484.
[7] R. D. Süssmuth, S. Pelzer, G. Nicholson, T. Walk, W. Wohlleben, G.
Jung, Angew. Chem. 1999, 111, 2096 ± 2099; Angew. Chem. Int. Ed.
1999, 38, 1976 ± 1979.
[8] S. Pelzer, R. Süssmuth, D. Heckmann, J. Recktenwald, P. Huber, G.
Jung, W. Wohlleben, Antimicrob. Agents Chemother. 1999, 1565 ±
1573.
[9] The M-configuration of the C-O-D ring was deduced from the
diagnostic NOE interactions given in the supplementary material of
D. L. Boger, S. Miyazaki, O. Loiseleur, R. T. Beresis, S. L. Castle, J. H.
Wu, Q. Jing, J. Am. Chem. Soc. 1998, 120, 8920 ± 8926.
the example of 4-octene as a substrate. The catalyst and the
reaction conditions must be coordinated so that a dynamic
kinetic control of the reaction, based on isomerization to the
thermodynamically less stable terminal olefin (step b) occurs
and that this olefin rapidly undergoes the final n-regioselec-
tive hydroformylation step (d). The formation of the isomeric
aldehydes (a, c) is thus suppressed.
Recently van Leeuwen et al. reported that with xantphos-
type diphosphines rhodium catalysts gave n-nonanal in 86%
regioselectivity from (E)-4-octene.[2] The low isomerization
activity of the catalyst however, resulted in turnover frequen-
[10] J. W. Trauger, C. T. Walsh, Proc. Natl. Acad. Sci. USA 2000, 97, 3112 ±
3117.
[11] D. P. OꢁBrian, P. N. Kirkpatrick, S. W. OꢁBrian, T. Staroske, T. I.
Richardson, D. A. Evans, A. Hopkinson, J. B. Spencer, D. H. Williams,
Chem. Commun. 2000, 103 ± 104.
[*] Dr. D. Selent, Prof. Dr. A. Börner
Institut für Organische Katalyseforschung an der
Universität Rostock e.V.
Buchbinderstrasse 5 ± 6, 18055 Rostock (Germany)
Fax : (49)381-46693-24
Dr. D. Hess, Dr. K.-D. Wiese, Dr. D. Röttger
Oxeno Olefinchemie GmbH, Marl (Germany)
Dipl.-Chem. C. Kunze
Institut für Anorganische und Analytische Chemie
Technische Universität Braunschweig (Germany)
Supporting information for this article is available on the WWW under
1696
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
1433-7851/01/4009-1696 $ 17.50+.50/0
Angew. Chem. Int. Ed. 2001, 40, No. 9