Cis,cis-Spiro[4.4]nonane-1,6-diol: A new chiral auxiliary for the asymmetric Diets-Alder reaction

Tetrahedron Asymmetry

Volumn 7, Issue 12, 1996, Pages 3521-3526

  Nieman, James A ^a   Keay, Brian A ^a  

^a UNIVERSITY OF CALGARY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

SPIRO COMPOUND;

ARTICLE; CHEMICAL REACTION; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030561245     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(96)00459-4     Document Type: Article

References (25)

1. 1. (a) Santelli, W.; Pons, J.-M. Lewis Acids and Selectivity in Organic Synthesis, CRC Press: New York; 1996; pg 267.
2. (b) Blaser, H.-U. Chem. Rev. 1992, 92, 935.
3. (c) Kagan, H.B., Riant, O. Chem. Rev. 1992, 92, 1007.
4. (d) Pindur, U.; Lutz, G.; Otto, C. Chem. Rev. 1993, 93, 741.
5. (e) Oppolzer, W. Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency in Modern Organic Chemistry; Trost, B. M., Ed.; Pergamon Press: Oxford, 1991; pg 315.
6. (f) Whitesell, J.K. Chem. Rev. 1989, 89, 1581.
7. (g) Carruthers, W. Cycloaddition Reactions in Organic Synthesis, Baldwin, J. E., Ed., Pergamon Press: Oxford, 1990; Chapters 3.
8. 2. Nieman, J.A.; Parvez, M.; Keay, B.A. Tetrahedron: Asymm. 1993, 4, 1973. For proof of the absolute configuration of (-)-1, see: Nieman, J.A.; Keay, B.A., Kubicki, M.; Yang, D.; Rauk, A., Tsankov, D.; Wieser, H. J. Org. Chem. 1995, 60, 1918. For the synthesis and resolution of a similar spirobiindane-1,1′-diol, see: Nieman, J.A.; Keay, B.A. Tetrahedron: Asymm. 1995, 6, 1575.
9. 2. Nieman, J.A.; Parvez, M.; Keay, B.A. Tetrahedron: Asymm. 1993, 4, 1973. For proof of the absolute configuration of (-)-1, see: Nieman, J.A.; Keay, B.A., Kubicki, M.; Yang, D.; Rauk, A., Tsankov, D.; Wieser, H. J. Org. Chem. 1995, 60, 1918. For the synthesis and resolution of a similar spirobiindane-1,1′-diol, see: Nieman, J.A.; Keay, B.A. Tetrahedron: Asymm. 1995, 6, 1575.
10. 2. Nieman, J.A.; Parvez, M.; Keay, B.A. Tetrahedron: Asymm. 1993, 4, 1973. For proof of the absolute configuration of (-)-1, see: Nieman, J.A.; Keay, B.A., Kubicki, M.; Yang, D.; Rauk, A., Tsankov, D.; Wieser, H. J. Org. Chem. 1995, 60, 1918. For the synthesis and resolution of a similar spirobiindane-1,1′-diol, see: Nieman, J.A.; Keay, B.A. Tetrahedron: Asymm. 1995, 6, 1575.
11. 4 in the asymmetric reduction of aromatic ketones, see: Srivastava, N.; Mital, A.; Kumar, A. J. Chem. Soc., Chem. Commun. 1992, 493. Attempts to repeat these results by both our and Seebach's groups have failed, see: Seebach, D.; Beck, A.K.; Dahinden, R.; Hoffmann, M., Kuhnle, F.N.M. Croatica Chemica Acta, 1996, 69, 459.
12. 4 in the asymmetric reduction of aromatic ketones, see: Srivastava, N.; Mital, A.; Kumar, A. J. Chem. Soc., Chem. Commun. 1992, 493. Attempts to repeat these results by both our and Seebach's groups have failed, see: Seebach, D.; Beck, A.K.; Dahinden, R.; Hoffmann, M., Kuhnle, F.N.M. Croatica Chemica Acta, 1996, 69, 459.
13. 4. For some examples of other diols which have been used as substrate bound chiral auxiliaries in the Diels-Alder reaction, see reference 1 and: (a) Oppolzer, W. Angew Chem. Int. Ed. Engl. 1984, 23, 876.
14. (b) Evans, D. A.; Chapman, K. T.; Bisaha, J. J. Am. Chem. Soc. 1988, 110, 1238.
15. (c) Gras, J.-L., Pellissier, H. Tetrahedron Lett. 1991, 32, 7043.
16. (d) Bezuldenhoudt, B.C.B.; Castle, G.H.; Geden, J.V.; Ley, S.V. Tetrahedron Lett. 1994, 55, 7451.
17. (e) Maitra, U.; Mathivanan P. J. Chem. Soc., Chem. Commun. 1993, 1469.
18. (f) Mathivanan, P.; Maitra, U.J. Org. Chem. 1995, 60, 364.
19. 2. The isolated yield of 4 was low (48% for entry 17) when 25 equivalents of cyclopentadiene was used, due to polymer formation. The isolated yield of 4 was increased (89%, 72%, 84% and 77% for entries 11, 17, 18, and 19 respectively), with no loss of de, if only 3 equiv. of cyclopentadiene were used.
20. 6. There are three diastereomers possible (assuming only the endo adduct is formed) from the Diels-Alder reaction with the bis-acrylate ester system, since two new asymmetric bicyclo adducts are formed per bisacrylate-diol. The absolute stereochemistry at C-2 of the bicylco adduct can have the following absolute configurations in the bisadduct-diol products: a) both S; b) one S and one R, and c) both R. Our analysis of the two diastereomers formed indicated that products a) and b) above were formed in a ratio of approximately 88:12 (∼75% de). lodolactonization of the two diastereomers provided iodolactones 5 in a ratio of 188:12 (1S,4S,6S,8R,9S:1R,4R,6R,8S,10R), which is consistent with the 89% ee observed.
21. 10 with respect to the assignment of the absolute configuration to spiro-systems such as compound 1 (formally a (ab)C(ab) system). The spiro-carbon atom is treated as a chiral centre and not as an axis of chirality. Thus, the spiro centre in compound 1 (Scheme 1) has an R configuration. For further information, see: Cahn, R.S.; Ingol, C.; Prelog, V. Angew. Chem. Int. Ed. Eng. 1966, 5, 385.
22. 4f
23. D +112.4 (c 2.83, benzene) for entry 19.
24. 10. Chan, A.S.C.; Lin, C-C.; Sun, J.; Hu, W.; Li, Z.; Pan, W.; Mi, A.; Jiang, Y.; Huang, T.-M.; Yang, T-K.; Chen, J-H.; Wang, Y.; Lee, G.-H. Tetrahedron: Asymm. 1995, 6, 2953.
25. 11. Waldmann, H. Liebigs Ann. Chem. 1990, 671.