Total Synthesis and Establishment of the Stereochemistry of Spiniferin-1, a Rare Planar Chiral Marine Natural Product with a 1,6-Methano[10]annulene Skeleton

Dedicated to Professors Weishan Zhou and Qingjiang Liao on their 90th birthdays

Abstract

Spiniferin-1, a rare planar chiral natural product with a 1,6-methano[10]annulene skeleton, has been synthesized via a novel polyfluoroalkanosulfonyl fluoride induced cascade carbocation rearrangement reaction. Natural spiniferin-1 was established as a racemic mixture by comparing its specific rotation with those of our synthesized S_p -(+)-spiniferin-1 and its R_p -(–)-enantiomer.

Key words

spiniferin-1 - planar chirality - total synthesis - rearrangement - annulenes

• References

• 1a Blunt JW, Copp BR, Hu WP, Munro MH. G, Northcote PT, Prinsep MR. Nat. Prod. Rep. 2009; 26: 170
• 1b Blunt JW, Copp BR, Munro MH. G, Northcote PT, Prinsep MR. Nat. Prod. Rep. 2010; 27: 165
• 2a Cimino G, Destefano S, Minale L, Trivellone E. Tetrahedron Lett. 1975; 3727
• 2b Cimino G, Destefano S, Minale L, Trivellone E. Experientia 1978; 34: 1425
• 3a Marshall JA, Conrow RE. J. Am. Chem. Soc. 1980; 102: 4274
• 3b Marshall JA, Conrow RE. J. Am. Chem. Soc. 1983; 105: 5679
• 4a Vogel E, Roth HD. Angew. Chem., Int. Ed. Engl. 1964; 3: 228
• 4b Vogel E, Böll WA. Angew. Chem., Int. Ed. Engl. 1964; 3: 642
• 4c Vogel E. Pure Appl. Chem. 1982; 54: 1015
• 5a Marinho AM. D, Rodrigues E, Ferreira AG, Santos LS. J. Braz. Chem. Soc. 2005; 16: 1342
• 5b Amagata T, Amagata A, Tenney K, Valeriote FA, Lobkovsky E, Clardy J, Crews P. Org. Lett. 2003; 5: 4393
• 5c Kozlovsky AG, Zhelifonova VP, Ozerskaya SM, Vinokurova NG, Adanin VM, Grafe U. Pharmazie 2000; 55: 470
• 6a Zhu Z, Tian WS, Liao QJ. Tetrahedron Lett. 1996; 37: 8553
• 6b Feng XS, Tian WS, Cheng QY. Bioorg. Med. Chem. Lett. 1997; 7: 3113
• 6c Zhu Z, Tian WS, Liao QJ, Wu YK. Bioorg. Med. Chem. Lett. 1998; 8: 1949
• 6d Feng XS, Tian WS, Cheng QY. J. Chem. Soc., Perkin Trans. 1 1998; 1139
• 6e Tian WS, Lei Z, Chen L, Huang Y. J. Fluorine Chem. 2000; 101: 305
• 6f Yan ZH, Wang J, Tian WS. Tetrahedron Lett. 2003; 44: 9383
• 6g Yan ZH, Tian WS. Tetrahedron Lett. 2004; 45: 2211
• 6h Yan ZH, Tian WS, Zeng F, Dai Y. Tetrahedron Lett. 2009; 50: 2727
• 7a Chen L, Ding K, Tian WS. Chem. Commun. 2003; 838
• 7b Ding K, Sun YS, Tian WS. J. Org. Chem. 2011; 76: 1495
• 7c Sun YS, Ding K, Tian WS. Chem. Commun. 2011; 47: 10437
• 8a Burn D, Perrow V, Weston GO. Tetrahedron Lett. 1960; issue 30: 14
• 8b Burn D, Ducker JW, Ellis B, Hiscock AK, Leftwick AP, Peach CM, Petrow V, Williamson DM. J. Chem. Soc. 1963; 4242
• 9 Veysoglu T, Mitscher LA, Swayze JK. Synthesis 1980; 807
• 10 Hagiwara H, Uda H. J. Chem. Soc., Perkin Trans. 1 1984; 91
• 11a Agnello EJ, Laubach GD. J. Am. Chem. Soc. 1957; 79: 1257
• 11b Agnello EJ, Laubach GD. J. Am. Chem. Soc. 1960; 82: 4293
• 12 Akao H, Kiyota H, Nakajima T, Kitahara T. Tetrahedron 1999; 55: 7757
• 13a Suryawanshi SN, Fuchs PL. J. Org. Chem. 1986; 51: 902
• 13b Chiu CK. F, Govindan SV, Fuchs PL. J. Org. Chem. 1994; 59: 311
• 14a Akiyama T, Katoh T, Mori K. Angew. Chem. Int. Ed. 2009; 48: 4226
• 14b Christoffers J, Rossler U, Werner T. Eur. J. Org. Chem. 2000; 701
• 14c Sasai H, Emori E, Arai T, Shibasaki M. Tetrahedron Lett. 1996; 37: 5561
• 15a Seebach D, Beck AK, Heckel A. Angew. Chem. Int. Ed. 2001; 40: 92
• 15b Toda F, Tanaka K. Tetrahedron Lett. 1988; 29: 551
• 16a Evarts Jr JB, Fuchs PL. Tetrahedron Lett. 2001; 42: 3673
• 16b Tsuji J, Yamakawa T, Kaito M, Mandai T. Tetrahedron Lett. 1978; 2075
• 17 Vogel E, Schieb T, Schulz WH, Schmidt K, Schmickler H, Lex J. Angew. Chem., Int. Ed. Engl. 1986; 25: 723

For detailed data, see:
• 18a Tian WS, Ding K. Chinese Patent CN1239492C, 2004
• 18b Tian WS, Ding K. Chinese Patent CN1199962C, 2004
• 19 He L, Xiang H, Zhang LY, Tian WS, He HH. Drug Dev. Res. 2005; 64: 203