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Facile, Novel Methodology for the Synthesis of
Spiro[pyrrolidin-3,3'-oxindoles]: Catalyzed
Ring Expansion Reactions of Cyclopropanes by
Aldimines**
Phil B. Alper, Christiane Meyers, Andreas Lerchner,
Dionicio R. Siegel, and Erick M. Carreira*
The spiro[pyrrolidin-3,3'-indole] ring system is a recurring
structural motif in a number of natural products such as
vinblastine and vincristine that function as cytostatics and are
of prime importance in cancer chemotherapy.[1] The related
spiro[pyrrolidin-3,3'-oxindole] ring system has been identified
in a number of other cytostatic alkaloids, exemplified by
spirotryprostatin A and strychnophylline.[2] Moreover, these
structures embody stereochemical and structural complexities
that continue to challenge the synthetic chemist.[3, 4] In
combination, these factors have driven the development of
novel, versatile, and efficient methods aimed at the synthesis
of the spiro[pyrrolidin-3,3'-oxindole] moiety and related
structures, as exemplified recently in the elegant total syn-
thesis of spirotryprostatin by Danishefsky et al. and of
aspidophytine by Corey et al.[5] We have been interested in
the development of a variety of methods for the stereo-
controlled synthesis of alkaloids.[6] Herein we report a novel
ꢀ
[16] A metal-assisted pentamerization of tBuC P to a metal-free penta-
mer starting from (h4-1-methylnaphthaline)(h6-toluene)iron was de-
scribed by U. Zenneck et al.: D. Hu, H. Schäufele, H. Pritzkow, U.
Zenneck, Angew. Chem. 1989, 101, 929; Angew. Chem. Int. Ed. Engl.
1989, 28, 900; D. Böhm, D. Hu, U. Zenneck, Phosphorus Sulfur Silicon
1993, 77, 5.
[17] a) M. Scheer, K. Schuster, T. A. Budzichowski, M. H. Chisholm, W. E.
Streib, J. Chem. Soc. Chem. Commun. 1995, 1671; b) M. Scheer, P.
Kramkowski, K. Schuster, Organometallics 1999, 18, 2874; c) P.
Kramkowski, G. Baum, U. Radius, M. Kaupp, M. Scheer, Chem. Eur.
J. 1999, 5, 2890.
[18] X-ray crystal structure data for 2 ´ C7H8: Stoe IPDS diffractometer,
MoKa (l 0.71069 ), structure solution with direct methods, least-
squares method, all non-hydrogen atoms were anisotropically refined.
The hydrogen atoms were fixed in idealized positions and refined
isotropically as riding models. C63H55O13P5W3 ´ C7H8, Mr 1818.60,
3
Å
crystal dimensions 0.45 Â 0.19 Â 0.08 mm , triclinic, space group P1
(no. 2); a 15.985(3), b 16.797(3), c 17.358(4) , a 90.99(3), b
111.35(3), g 116.62(3)8, T 200(1) K, Z 2, V 3788.5(13) 3,
3
1
1calcd 1.594 Mgm
,
m(MoKa) 47.05 cm
; of 13638 independent
reflections (2qmax 538), 12004 were observed with Fo 4s(Fo); 900
parameters, R1 0.0361, wR2 0.1069; structure solution and refine-
ment with the programs SHELXS-86[28a] and SHELXL-93.[28b]
Crystallographic data (excluding structure factors) for the
structure reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publica-
tion no. CCDC-125116. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge
CB21EZ, UK (fax: (44)1223-336-033; e-mail: deposit@ccdc.cam.
ac.uk).
[*] Prof. Dr. E. M. Carreira, Dr. P. B. Alper, C. Meyers, A. Lerchner
Laboratorium für Organische Chemie, ETH-Zentrum
Universitätstrasse 16, CH-8092 Zürich (Switzerland)
Fax : ( 41)1-632-13-28
D. R. Siegel
Arnold and Mabel Beckman Laboratory for Chemical Synthesis
California Institute of Technology
Pasadena, CA 91125 (USA)
[19] For seven-coordinate W atoms, see also K. W. Chiu, D. Lyons, G.
Wilkinson, M. Thornton-Pett, M. B. Hursthouse, Polyhedron 1983, 2,
803; R. M. Laine, R. E. Moriarty, R. Bau, J. Am. Chem. Soc. 1972, 94,
1402; G. Huttner, J. Borm, L. Zsolnai, J. Organomet. Chem. 1986, 304,
309.
[**] We thank the ETH, Kontaktgruppe für Forschungsfragen (KGF), and
Hoffmann-La Roche AG for their generous support.
Supporting information for this article is available on the WWW
3186
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1433-7851/99/3821-3186 $ 17.50+.50/0
Angew. Chem. Int. Ed. 1999, 38, No. 21