A chiral biselectrophile for efficient asymmetric synthesis in water

Green Chemistry

Volumn 7, Issue 5, 2005, Pages 259-261

  Hidestål, Olle ^a   Ding, Rui ^a   Almesåker, Ann ^a   Lindström, Ulf M ^a  

^a LUND UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

1,6 BISELECTROPHILE; CHEMICAL COMPOUND; ORGANIC COMPOUND; SOLVENT; TETRAHYDROFURAN; UNCLASSIFIED DRUG; WATER;

ASYMMETRIC SYNTHESIS; CHIRALITY; CONFERENCE PAPER; POLYMERIZATION;

EID: 19744379924     PISSN: 14639262     EISSN: 14639270     Source Type: Journal    
DOI: 10.1039/b415300f     Document Type: Conference Paper

References (18)

1. (a) U. M. Lindström, Chem. Rev., 2002, 102, 2751-2771;
2. (b) Organic Synthesis in Water, ed. P. A. Grieco, Blackie Academic & Professional, London, 1998;
3. (c) C. J. Li and T. H. Chan, Organic Reactions in Aqueous Media, John Wiley & Sons, New York, 1997.
4. C. W. Spangler, R. K. McCoy, A. A. Dembek, L. S. Sapochak and B. D. Gates, J. Chem. Soc., Parkin Trans. 1, 1989, 151-154.
5. (a) H. C. Kolb, Y. L. Bennani and K. B. Sharpless, Tetrahedron: Asymmetry, 1993, 4, 133-141;
6. (b) K. P. M. Vanhessche, Z. M. Wang and K. B. Sharpless, Tetrahedron Lett., 1994, 35, 3469-3472.
7. Attempts to synthesize the corresponding 1,6-dichlorodiene failed because polymerization could not be avoided. Only a theoretical report of this compound exists in the literature: G. Park, Bull. Korean Chem. Soc., 2003, 24, 265-266.
8. Apart from traces of epoxide 3, the only observable contamination after the modified work-up procedure is 1-5% of methansulfonamide. The ee of 2 was determined by chiral HPLC using a Chiralpak AD-H column with 15% tert-butanol in heptane as eluent. The major isomer eluted at 32 min and the minor at 28 min. A reference sample containing both enantiomers was prepared by performing the AD reaction with equal amounts of α- and β-mix. The use of tert-butanol as co-eluent is crucial. Other alcohols gave decomposition of 2 on the column.
9. H. C. Kolb, M. S. VanNieuwenhze and K. B. Sharpless, Chem. Rev., 1994, 94, 2483-2547.
10. Epoxide 3 is more labile than the starting dibromide and any unnecessary storage and handling should be avoided.
11. C. J. Li and T. H. Chan, Tetrahedron, 1999, 55, 11149-11176.
12. For another indium mediated allylation using highly functionalized allyl bromides, see: Y. Canac, E. Levoirier and A. Lubineau, J. Org. Chem., 2001, 66, 3206-3210.
13. (a) H. Araya, M. Sahai, S. Singh, A. K. Singh, M. Yoshida, N. Hara and Y. Fujimoto, Phytochemistry, 2002, 61, 999-1004;
14. (b) E. Peris, A. Cavé, E. Estornell, M. C. Zafra-Polo, B. Figadère, D. Cortes and A. Bermejo, Tetrahedron, 2002, 58, 1335-1342;
15. (c) S. H. Sung, M. S. Huh and Y. C. Kim, Chem. Pharm. Bull., 2001, 49, 1192-1194.
16. (a) S. M. Miles, S. P. Marsden, R. J. Leatherbarrow and W. J. Coates, J. Org. Chem., 2004, 69, 6874-6882;
17. (b) P. K. Mandal, G. Maiti and S. C. Roy, J. Org. Chem., 1998, 63, 2829-2834;
18. (c) Z. M. Wang and M. Shen, J. Org. Chem., 1998, 63, 1414-1418.