Abstract
The synthetic method of the novel chiral synthon, 5-l-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucleophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR,1H NMR,13C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(l-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2,3′-(4′-/-menthyloxy-5′-l-menthyloxybutyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex molecules containing spiro-cyclopropane skeleton with multiple chiral centers.
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References
Seyden-Penne, J. (ed)., Chiral Auxiliaries and Ligands in Asymmetric Synthesis, New York: John Wiley & Sons. Inc., 1995, p.43.
Van Oeveren. A., Jansen, J. F. G. A., Feringa, B. L., Enantioselective synthesis of natural dibenzybutyrolactone lignans(-)- enteroctone, (-)-hinokinin, (-)pluviatolide, (-)-enterodiol and furofuran lignan(-)-eudesmi via tandem conjugate addition to Y-alkoxybutenolides, J. Org. Chem., 1994, 59: 5999.
Pelter, A., Ward, R. S., Jones, D. M. et al., Asymmetric syntheses of ligands of the dibenzyl-butyrolactone, dibenzylbutanediol. aryltetralin and dibenzocyclooctadiene series, Tetrahedron: Asymmetry, 1992, 3(2): 239.
Wang Yuhai, Chen Qinghua, Studies on the synthesis of novel chiral compounds of purine and pyrimidine bases, Science in China, Ser. B, 1999, 42(2): 121.
Chen Qinghua, Zhou Chang, Industrial synthesis of optically active compounts, Youji Huaxue (Organic Chemistry, in Chinese). 1994, 14: 1.
Chen Qinghua, Huang Bin, Synthesis of a novel chiral source using borneol as auxiliary and its sterospecific reaction, Chinese Science Bulletin (in Chinese), 1994, 39: 2154.
Chen Qinghua, Gen Zhe, Huang Bin, Synthesis of enantiomerically pure 5-(l-menthyloxy)-3,4-dibromo-2(5H)-furanone and its tandem asymmetric Michael addition-elimination reaction, Tetrahedron: Asymmetry, 1995, 6: 401.
Huang Hui, Chen Qinghua, Synthesis of enantiomerically pure 5-(l-menthyloxy)-3,4-dibromo-2(5H)-furanone and its tandem asymmetric Michael addition-elimination reaction, Tetrahedron: Asymmetry, 1998, 9: 4103.
Huang Hui, Chen Qinghua, Synthesis of spiro-cyclopropane derivatives containing multiple chiral centers, Science in China, Ser. B, 1999, 42, (3): 268.
Huang Hui, Chen Qinghua, Synthesis and structure of the chiral spiro-cyclopropane derivatives, Acta Chimica Sinica (in Chinese). 1999, 57: 641.
Huang Hui, Chen Qinghua, A valuable synthetic route to spiro-cyclopropane derivatives containing multiple stereogenic centers, Tetrahedron: Asymmetry, 1999, 10: 1295.
Farina, F., Maestro, M. C., Martin, M. R., Pseudoesters and derivatives (XXIII)—Reaction of 3-bromo-5-methoxyfuran- 2(5H)-one with nucleophiles, Tetrahedron, 1986, 42(13): 3715.
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Huang, H., Chen, Q. Approach to synthesis of novel chiral 3-chloro-2(5H)-furanone and its application in asymmetric reactions. Chin.Sci.Bull. 45, 711–716 (2000). https://doi.org/10.1007/BF02886175
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DOI: https://doi.org/10.1007/BF02886175