Concise Enantioselective Synthesis of Furan Lignans (-)-Dihydrosesamin and (-)-Acuminatin and Furofuran Lignans (-)-Sesamin and (-)-Methyl Piperitol by Radical Cyclization of Epoxides

Biplab Banerjee; Subhas Chandra Roy

doi:10.1055/s-2005-872173

PAPER

Concise Enantioselective Synthesis of Furan Lignans (-)-Dihydrosesamin and (-)-Acuminatin and Furofuran Lignans (-)-Sesamin and (-)-Methyl Piperitol by Radical Cyclization of Epoxides

Biplab Banerjee, Subhas Chandra Roy*
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India
Fax: +91(33)24732805; e-Mail: ocscr@mahendra.iacs.res.in;

Abstract

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Abstract

Enantioselective syntheses of furan lignans (-)-dihydrosesamin and (-)-acuminatin and furofuran lignans (-)-sesamin and (-)-methyl piperitol were achieved in up to only three steps in 43%, 42%, 63%, and 60% overall yield, respectively, with high optical purity through stereoselective intramolecular radical cyclization of suitably substituted epoxy olefinic ethers using bis(cyclopentadienyl)titanium(III) chloride as the radical initiator. The key intermediate, chiral epoxy alcohol 4, was prepared by the Sharpless kinetic resolution method. The titanium(III) initiator was prepared in situ from commercially available titanocene dichloride and activated zinc dust in tetrahydrofuran.

Key words

enantioselectivity - lignans - radical cyclizations - transition metals - titanium

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Referenzen

References

1a Rao CBS. Chemistry of lignans Andhra University Press; Andhra, India: 1978.

1b Whiting DA. Nat. Prod. Rep. 1985, 2: 191

1c Whiting DA. Nat. Prod. Rep. 1987, 4: 499

1d Whiting DA. Nat. Prod. Rep. 1990, 7: 349

1e Ward RS. Nat. Prod. Rep. 1993, 10: 1

1f Ward RS. Nat. Prod. Rep. 1995, 12: 183

2a Gottlieb OR. In New Natural Products and Plant Drugs with Pharmacological, Biological or Therapeutic Activity Springer; Berlin: 1987. p.227

2b MacRae WD. Towers GHN. Phytochemistry 1984, 23: 1207 ; and references cited therein

3 Lin-Gen Z. Seligmann O. Lotter H. Wagner H. Phytochemistry 1983, 22: 265

4 Ward RS. Nat. Prod. Rep. 1997, 14: 43 ; and references cited therein

5 Bertram SH. Vander der steur JPK. Waterman HI. Biochem. Z. 1928, 1: 197

6a Hoke M. Hansel R. Arch. Pharm. (Weinheim, Ger.) 1972, 33: 305

6b Pan J.-X. Hensens OD. Zink DL. Chang MN. Hwang S.-B. Phytochemistry 1987, 26: 1377

7a Stevens DR. Whiting DA. J. Chem. Soc., Perkin Trans. 1 1990, 425

7b Stevens DR. Whiting DA. J. Chem. Soc., Perkin Trans. 1 1992, 633

7c Pelter A. Ward RS. Venkateswarlu R. Kamakshi C. Tetrahedron 1991, 47: 1275

7d Beroza M. Schechter MS. J. Am. Chem. Soc. 1956, 78: 1242

7e Orito K. Yorita K. Suginome H. Tetrahedron Lett. 1991, 32: 5999

7f Bradley HM. Knight DW. J. Chem. Soc., Chem. Commun. 1991, 1641

7g Takano S. Samizu K. Ogasawara K. J. Chem. Soc., Chem. Commun. 1993, 1032

7h Orito K. Sasaki T. Suginome H. J. Org. Chem. 1995, 60: 6208 ; and references cited therein

8 Yamauchi S. Tanaka T. Kinoshita Y. J. Chem. Soc., Perkin Trans. 1 2001, 2158

9 Takano S. Ohkawa T. Tamori S. Satoh S. Ogasawara K. J. Chem. Soc., Chem. Commun. 1988, 189

10 Oeveren A. Jansen JFGA. Feringa BL. J. Org. Chem. 1994, 59: 5999

11 Kise N. Fujimoto A. Ueda N. Tetrahedron: Asymmetry 2002, 13: 1845

12 Enders D. Lausberg V. Signore GD. Berner OM. Synthesis 2002, 515

13a Wirth T. Kulicke KJ. Fragale G. J. Org. Chem. 1996, 61: 2686

13b Wirth T. Liebigs Ann./Recl. 1997, 1155

13c Brown RCD. Swain NA. Synthesis 2004, 811

14 Samizu K. Ogasawara K. Chem. Lett. 1995, 543

15a Rana KK. Guin C. Roy SC. Tetrahedron Lett. 2000, 41: 9337

15b Roy SC. Rana KK. Guin C. J. Org. Chem. 2002, 67: 3242

16a Ueno Y. Chino K. Watanabe M. Moriya O. Okawara M. J. Am. Chem. Soc. 1982, 104: 5564

16b Stork G. Mook R. Biller SA. Rychnovskyu SD. J. Am. Chem. Soc. 1983, 105: 3741

17a Rajanbabu TV. Nugent WA. J. Am. Chem. Soc. 1994, 116: 986 ; and references cited therein

17b Gansäuer A. Bluhm H. Chem. Rev. 2000, 100: 2771

17c Gansäuer A. Pierobon M. Bluhm H. Synthesis 2001, 2500

18 Srikrishna A. Yelamaggad CV. Kumar PP. J. Chem. Soc., Perkin Trans. 1 1999, 2877

19a Gao Y. Hanson RM. Klunder JM. Ko SY. Masamune H. Sharpless KB. J. Am. Chem. Soc. 1987, 109: 5765 ; and references cited therein

19b Procter G. Asymmetric Synthesis Oxford University Press Inc.; New York: 1996. p.178

20a Searle PA. Molinski TF. J. Am. Chem. Soc. 1996, 118: 9422

20b Mohapatra DK. Yellol GS. ARKIVOC 2005, iii: 144

21 Tanaka H. Nakamura T. Ichino K. Ito K. Phytochemistry 1989, 28: 952

22a Ina H. Asai A. Ushida T. Planta Med. 1987, 228

22b Greger H. Hofer O. Tetrahedron 1980, 36: 3551

23 Hansel R. Zander D. Arch. Pharm. 1961, 294: 699

24 Iida T. Nakano M. Ito K. Phytochemistry 1982, 21: 673