Chiral induction by elimination-coupled lithium-ene reaction: Synthesis of (+)-(3R,4R)-1,2-dihydromultifidene

Angewandte Chemie - International Edition

Volumn 38, Issue 4, 1999, Pages 546-548

  Deiters, Alexander ^a   Hoppe, Dieter ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

Asymmetric synthesis; Carbocycles; Ene reactions; Metalations

Indexed keywords

1,2 DIHYDROMULTIFIDENE; ALKADIENYL CARBAMATE; CHIRALITY; CYCLIZATION; DIVINYLCYCLOPENTANE; ENANTIOSELECTIVITY; LITHIUM; SPARTEINE;

1,2 DIHYDROMULTIFIDENE; CARBAMIC ACID DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033558172     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(sici)1521-3773(19990215)38:4<546::aid-anie546>3.0.co;2-%23     Document Type: Article

References (40)

1. Review: W. Oppolzer, Angew. Chem. 1989, 101, 39-53;
2. Angew. Chem. Int. Ed. Engl. 1989, 28, 38-52.
3. A. D. Josey, J. Org. Chem. 1974, 39, 139-145.
4. H. Felkin, J. D. Umpleby, E. Hagaman, E. Wenkert, Tetrahedron Lett. 1972, 2285-2288.
5. A single example of a Pd-ene reaction induced by a chiral ligand has been described (47% ee, cis:trans = 87:13): W. Oppolzer, D. L. Kuo, M. W. Hutzinger, R. Léger, J.-O. Durand, C. Leslie, Tetrahedron Lett. 1997, 38, 6213-6216.
6. a) O. Zschage, D. Hoppe, Angew. Chem. 1989, 101, 67-69;
7. Angew. Chem. Int. Ed. Engl. 1989, 28, 67-69;
8. b) O. Zschage, D. Hoppe, Tetrahedron 1992, 48, 8389-8392;
9. c) H. Paulsen, C. Graeve, D. Hoppe, Synthesis 1996, 141-144.
10. Reviews: a) D. Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376-2410;
11. Angew. Chem. Int. Ed. Engl. 1997, 36, 2282-2316;
12. b) P. Beak, A. Basu, D. J. Gallagher, Y. S. Park, S. Thayumanavan, Acc. Chem. Res. 1996, 29, 552-560.
13. 1H NMR coupling constants of the alkene protons (15.7 and 15.2 Hz)
14. [10]
15. a) J. Villieras, M. Raumbaud, M. Graff, Synth. Commun. 1986, 16, 149-156;
16. b) F. Hintze, D. Hoppe, Synthesis 1992, 1216-1218.
17. A. Deiters, Diplomarbeit, Universität Münster, 1998.
18. 1H NMR coupling constants of the alkene protons at 6.5 Hz. The enantiomeric ratio was determined by gas chromatography on a chiral stationary phase (Beta-Dex 120, Supelco, USA).
19. Compound rac-8a is also obtained in 90% yield with nBuLi/TMEDA. At least two equivalents of base are required because 8a is deprotonated to 8e under the reaction conditions: B. Peschke, Dissertation, Kiel University, 1991;
20. S. Sengupta, V. Snieckus, J. Org. Chem. 1990, 55, 5680-5683;
21. H. Paulsen, D. Hoppe, Tetrahedron 1992, 48, 5667-5670 and reference [13].
22. P. Kocienski, N. J. Dixon, Synlett 1989, 52-54;
23. P. Kocienski, C. Barber, Pure Appl. Chem. 1990, 62, 1933-1940.
24. W. Boland, K. Mertes, L. Jaenicke, D. G. Müller, E. Fölster, Helv. Chim. Acta 1983, 66, 1905-1913.
25. [14]
26. 3).
27. D. Hoppe, M. Paetow, F. Hintze, Angew. Chem. 1993, 105, 430-432;
28. Angew. Chem. Int. Ed. Engl. 1993, 32, 394-396.
29. For precedences on inversion of configuration during silylation and stannylation reactions with allyllithium-(-)-sparteine complexes, see K. Behrens, Dissertation, Münster University 1997 and reference [5c].
30. For inversion of configuration of chiral benzyllithium compounds during stannylation (inversion) and lithium destannylation (retention), see A. Carstens, D. Hoppe, Tetrahedron 1994, 50, 6097-6108;
31. G. A. Weisenburger, P. Beak, J. Am. Chem. Soc. 1996, 118, 12218-12219 and reference [18].
32. The carbamoyloxy group in γ-monosubstituted lithiated allyl carbamates (e.g., 7) preferentially adopts the endo configuration, which leads to a 1Z double bond in the products (e.g., 8a): D. Hoppe, R. Hanko, A. Brönneke, F. Lichtenberg, E. von Hülsen, Chem. Ber. 1985, 118, 2822-2851.
33. +/(-)-sparteine is replaced by a less sterically congested lithium cation, which in turn leads to a higher rate of reaction. Control experiments with the addition of lithium chloride or lithium butoxide lead to an enantiomeric enrichment factor of up to 1.2; these results agree with the proposed reaction pathway.
34. We thank one of the referees for stimulating suggestions.
35. N′ reaction: E.-U. Würthwein, C. Mück-Lichtenfeld, unpublished results.
36. Experiments (b) and (c) in Scheme 5 gave the cyclopentanes (+)-8a and (-)-8a in quantitative yields. If the lithium intermediates 7 and epi-7 were of unrestricted configurational stability, and if both complexes were to cyclize at the same rate, the same enantiomeric ratio would be expected in the product 8a as in respective educts 15 (74:26 and 50:50, respectively). In both cases a shift in favor of the product (+)-8a would be recorded; that is, 7 is involved to a greater extent in product formation than epi-7.
37. For the synthesis of enantiomer-enriched cyclopentanols by (-)-Sparteine-induced intramolecular carbolithiation, see M. J. Woltering, R. Fröhlich, D. Hoppe, Angew. Chem. 1997, 109, 1804-1805;
38. Angew. Chem. Int. Ed. Engl. 1997, 36, 1764-1765;
39. M. Oestreich, R. Fröhlich, D. Hoppe, Tetrahedron Lett. 1998, 39, 1745-1748.
40. All new compounds gave satisfactory elemental analyses (C,H,N; ±0.4).