An Expeditious Enantiospecific Total Synthesis of (+)-7-epi-Goniofufurone

Abstract

Stereoselective synthesis of styryl lactone, (+)-7-epi-goniofufurone was achieved in high yield via simple transformations from tartaric acid. The key step involves the successive stereoselective reduction of ketones with borohydride and selectride.

styryl lactones - (+)-goniofufurone - stereoselective reduction

References

1 For a review on styryllactones from Goniothalamus species see: Blàzquez MA. Bermejo A. Zafra-Polo MC. Cortes D. Phytochem. Anal.  1999,  10:  161 

2a Fang XP. Anderson JE. Chang CJ. Fanwick PE. McLaughlin JL. J. Chem. Soc., Perkin. Trans. 1  1990,  1655 

2b Fang XP. Anderson JE. Chang CJ. McLaughlin JL. Fanwick PE. J. Nat. Prod.  1991,  54:  1034 

2c Fang XP. Anderson JE. Chang CJ. McLaughlin JL. Tetrahedron  1991,  47:  9751 

3 For a review on the cytotoxic activity and other bioactivity of styryl lactones, see: Mereyala HB. Joe M. Curr. Med. Chem.: Anti-Cancer Agents  2001,  1:  293 

4a Ye J. Bhatt RK. Falck JR. Tetrahedron Lett.  1993,  34:  8007 

4b Murphy PJ. Dennison ST. Tetrahedron  1993,  49:  6695 

4c Gracza T. Jäger V. Synthesis  1994,  1359 

4d Xu D. Sharpless KB. Tetrahedron Lett.  1994,  35:  4685 

4e Yang ZC. Zhou WS. Tetrahedron  1995,  51:  1429 

4f Ko SY. Lerpiniere J. Tetrahedron Lett.  1995,  36:  2101 

4g Yi X.-H. Meng Y. Hua X.-G. Li C.-J. J. Org. Chem.  1998,  63:  7472 

4h Fernandez de la Pradilla R. Montero C. Priego J. Martinez-Cruz LA. J. Org. Chem.  1998,  63:  9612 

4i Bruns R. Wernicke A. Koll P. Tetrahedron  1999,  55:  9793 

4j Surivet J.-P. Vatele J.-M. Tetrahedron  1999,  55:  13011 

5 Shing TKM. Tsui HC. Zhou ZH. J. Org. Chem.  1995,  60:  3121 

6a Prakash KRC. Rao SP. Tetrahedron  1993,  49:  1505 

6b Prakash KRC. Rao SP. Synlett  1993,  123 

7 Mukai C. Kim IJ. Kido M. Hanaoka M. Tetrahedron  1996,  52:  6547 

8 Tsubuki M. Kanai K. Nagase H. Honda T. Tetrahedron  1999,  55:  2493 

9a Mereyala HB. Gadikota RR. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.  2000,  39:  166 

9b Mereyala HB. Gadikota RR. Joe M. Arora SK. Dastidar SG. Agarwal S. Bioorg. Med. Chem.  1999,  7:  2095 

10 Su Y.-L. Yang C.-S. Teng S.-J. Zhao G. Ding Y. Tetrahedron  2001,  57:  2147 

11a Toda F. Tanaka K. J. Org. Chem.  1988,  53:  3607 

11b Seebach D. Hidber A. Org. Synth., Coll. Vol. 7   Wiley; New York: 1990.  p.447 

12

The minor isomer was removed by simple crystallization from hexane-EtOAc.

13

We anticipated that the addition of vinyl magnesiumbromide to 9 followed by a stereoselective reduction of the ketone and RCM would yield the intermediate 14. However, addition of vinyl magnesium bromide to 9 proceeded with low yield. Full details of this strategy will be discussed in a future article.

14

All new compounds exhibited satisfactory spectral data. 8: [α]_D +23 (c 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 1.41 (s, 3 H), 1.50 (s, 3 H), 3.00 (s, 3 H), 3.17 (s, 3 H), 5.16 (d, J = 5.7 Hz, 1 H), 5.934 (d, J = 5.4 Hz, 1 H), 7.40-7.65 (m, 3 H), 8.05-8.15 (m, 2 H). ¹³C NMR (75 MHz): δ = 26.40, 35.97, 37.13, 75.04, 76.59, 77.43, 79.45, 112.56, 128.55, 129.41, 133.69, 134.94, 168.25, 196.38. Anal. calcd for C₂₁H₃₄NO₄Si: C, 64.97; H, 6.91. Found: C, 65.28; H, 7.02. 9: [α]_D +67.5 (c 1, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = -0.14 (s, 3 H), -0.04 (s, 3 H), 0.84 (s, 9 H), 1.26 (s, 3 H), 1.34 (s, 3 H), 2.84 (s, 3 H), 2.99 (s, 3 H), 4.44 (d, J = 6.6 Hz, 1 H), 4.72-4.88 (m, 2 H), 7.15-7.40 (m, 5 H). ¹³C NMR (75 MHz): δ = -5.15, -4.85, 18.21, 25.71, 26.43, 26.71, 35.78, 36.96, 73.23, 74.14, 82.03, 110.97, 127.29, 127.52, 127.71, 140.59, 169.04. Anal. calcd for C₂₁H₃₅NO₄Si: C, 64.08; H, 8.96. Found: C, 64.10; H, 9.21. 11: [α]_D +38.9 (c 1.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = -0.12 (s, 3 H), 0.00 (s, 3 H), 0.82 (s, 9 H), 1.10 (s, 3 H), 1.32 (s, 3 H), 1.33-1.50 (m, 1 H), 1.85-2.15 (m, 3 H), 3.09 (br s, 1 H), 3.64 (dd, J = 8.1 Hz, 2.4 Hz 1 H), 4.10 (dd, J = 8.1 Hz, 5.4 Hz 1 H), 4.76 (d, J = 5.1 Hz, 1H), 4.80-5.00 (m, 2 H), 5.67 (ddt, J = 16.8 Hz, 10.2 Hz, 6.9 Hz, 1 H), 7.15-7.30 (m, 5 H). ¹³C NMR (75 MHz): δ = -4.99, -4.85, 18.26, 25.79, 27.04, 27.39, 29.87, 33.87, 69.33, 75.54, 79.25, 80.57, 109.13, 114.79, 127.40, 127.78, 127.88, 138.14, 139.97. 13: [α]_D +11.7 (c 0.6, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 0.00 (s, 3 H), 0.11 (s, 3 H), 0.90 (s, 9 H), 1.17 (s, 3 H), 1.34 (s, 3 H), 3.87 (dd, J = 8.1, 2.4 Hz, 1 H), 4.46 (dd, J = 8.1, 5.7 Hz, 1 H), 4.52 (q, J = 2.0 Hz, 1 H), 4.94 (d, J = 5.7 Hz, 1 H), 6.07 (dd, J = 5.7 Hz, 1.8 Hz, 1 H), 7.26 (dd, J = 5.7, 1.8 Hz, 1 H), 7.25-7.45 (m, 5 H). ¹³C NMR (75 MHz): δ = -4.97, -4.94, 18.27, 25.79, 26.27, 26.99, 75.08, 75.11, 80.03, 81.47, 110.23, 122.14, 127.27, 128.03, 139.38, 153.10, 172.82. Anal. calcd for C₂₂H₃₃O₅Si: C, 65.31; H, 7.97. Found: C, 65.26; H, 7.80.