Synlett 2008(10): 1526-1528  
DOI: 10.1055/s-2008-1077788
LETTER
© Georg Thieme Verlag Stuttgart · New York

Formal Total Synthesis of Benzylpedamide: The Right Half of (+)-Pederin

Degang Liu, Jijun Xue, Zhixiang Xie, Liping Wei, Xianshu Zhang, Ying Li*
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China
Fax: +86(931)8912582; e-Mail: liying@lzu.edu.cn;
Further Information

Publication History

Received 5 February 2008
Publication Date:
16 May 2008 (online)

Abstract

The right half of (+)-pederin was synthesized through a convenient and efficient asymmetric synthesis in 14 steps with 8.3% overall yield. The key step was an iodine-induced heterocyclization to construct the pyran ring. The chiral centers were constructed separately via asymmetric allylation, substrate-controlled diastereoselective reactions, and Sharpless asymmetric dihydroxylation.

    References and Notes

  • 1a Piel J. Butzke D. Fusetani D. Hui D. Platzer M. Wen G. Matsunaga S. J. Nat. Prod.  2005,  68:  472 
  • 1b Cichewicz RH. Valeriote FA. Crews P. Org. Lett.  2004,  6:  1951 
  • 2a Ueta A. J. Kurume Med. Coll., Kyushu  1949,  249 
  • 2b Pavan M. Bo G. Physiol. Comput. Oecol.  1953,  3: 307; Chem. Abstr. 1954, 48, 57887
  • 3a Narquizian R. Kocienski P. In The Role of Natural Products in Drug Discovery   Mulzer J. Bohlmann R. Springer; New York: 2000.  p.25-56  
  • 3b Levine MR. Dancis J. Pavan M. Cox RP. Pediat. Res.  1974,  8:  606 
  • 4 Green ME. Rech JC. Floreancig PE. Org. Lett.  2005,  7:  4117 
  • For total synthesis of pederin compounds, see:
  • 5a Hong CY. Kishi Y. J. Org. Chem.  1990,  55:  4242 
  • 5b Hong CY. Kishi Y. J. Am. Chem. Soc.  1991,  113:  9693 
  • 5c Roush WR. Pfeifer LA. Org. Lett.  2000,  2:  859 
  • 5d Trost BM. Yang H. Probst GD. J. Am. Chem. Soc.  2004,  126:  48 
  • 5e Jiang X. Garcia-Fortanet J. De Brabander JK. J. Am. Chem. Soc.  2005,  127:  11254 
  • 5f For synthesis of the left halves, see: Huang X. Shao N. Palani A. Aslanian R. Buevich A. Org. Lett.  2007,  9:  2597 
  • 5g Adams MA. Duggan AJ. Smolanoff J. Meinwald J. J. Am. Chem. Soc.  1979,  101:  5364 
  • 5h Roush WR. Marron TG. Pfeifer LA. J. Org. Chem.  1997,  62:  474 
  • 5i For synthesis of the right halves, see: Breitfelder S. Schuemacher AC. Rolle T. Kikuchi M. Hoffmann RW. Helv. Chim. Acta  2004,  87:  1202 
  • 5j Hoffman RW. Schlapbach A. Tetrahedron  1992,  48:  1959 
  • 5k Marron T. Roush WR. Tetrahedron Lett.  1995,  36:  1581 
  • 5l Breitfelder S. Schlapbach A. Hoffmann RW. Synthesis  1998,  468 
  • 5m Jiang X. Williams N. DeBrabander JK. Org. Lett.  2007,  9:  227 
  • For total synthesis of pederin compounds, see:
  • 6a Matsuda F. Tomiyoshi N. Yanagiya M. Matsumoto T. Tetrahedron  1988,  44:  7063 
  • 6b For synthesis of the left halves, see: Tsuzuki K. Watanabe T. Yanagiya M. Matsumoto T. Tetrahedron Lett.  1976,  17:  4745 
  • 6c Yanagiya M. Matsuda F. Hasegawa K. Matsumoto T. Tetrahedron Lett.  1982,  23:  4039 
  • 6d Matsumoto T. Matsuda F. Hasagawa K. Yanagiya M. Tetrahedron  1984,  40:  2337 
  • For total synthesis of pederin compounds, see:
  • 7a Nakata T. Nagao S. Oishi T. Tetrahedron Lett.  1985,  26:  6465 
  • 7b Nakata T. Fukui H. Nakagawa T. Matsukura H. Heterocycles  1996,  42:  159 
  • 7c For synthesis of the left halves, see: Trotter NS. Nakata T. Org. Lett.  1999,  1:  957 
  • 7d Nakata T. Nagao S. Mori N. Oishi T. Tetrahedron Lett.  1985,  26:  6461 
  • 7e Nakata T. Matsukura H. Dunlong J. Nagashima H. Tetrahedron Lett.  1994,  35:  8229 
  • 7f Takemura T. Nishii Y. Takahashi S. Kobayashi J. Nakata T. Tetrahedron  2002,  58:  6359 
  • For total synthesis of pederin compounds, see:
  • 8a Willson T. Kocienski P. Faller A. Campbell S. J. Chem. Soc., Chem. Commun.  1987,  106 
  • 8b Willson TM. Kocienski P. Jarowicki K. Isaac K. Hitchcock PM. Faller A. Campbell SF. Tetrahedron  1990,  46:  1767 
  • 8c Kocienski P. Jarowicki K. Marczak S. Synthesis  1991,  1191 
  • 8d Kocienski P. Raubo P. Davis JK. Boyle FT. Davies DE. Richter A. J. Chem. Soc., Perkin Trans. 1  1996,  1797 
  • 8e Kocienski P. Narquizian R. Raubo P. Smith C. Farrugia LJ. Muir K. Boyle FT. J. Chem. Soc., Perkin Trans. 1  2000,  2357 
  • 8f For synthesis of the left halves, see: Willson TM. Kocienski P. Jarowicki K. Isaac K. Faller A. Campbell SF. Bordner J. Tetrahedron  1990,  46:  1757 
  • 8g For synthesis of the right halves, see: Kocienski P. Willson TM. J. Chem. Soc., Chem. Commun.  1984,  1011 
  • For total synthesis of pederin compounds, see:
  • 9a Sohn J. Waizumi N. Zhong HM. Rawal VH. J. Am. Chem. Soc.  2005,  127:  7290 
  • 9b John CJ. Rawal VH. Angew Chem. Int. Ed.  2007,  119:  6622 
  • 9c For synthesis of the right halves, see: Zhong HM. Sohn JH. Rawal HV. J. Org. Chem.  2007,  72:  386 
  • 10 Ihara M. Suzuki M. Fukunoto K. Kameani T. Kabuto C. J. Am. Chem. Soc.  1988,  110:  1963 
  • 11 Jadhav PK. Bhat KS. Perumal PT. Brown HC.
    J. Org. Chem.  1986,  51:  432 
  • 12 Heathcock CH. Kiyooka S. Blumenkopf TA. J. Org. Chem.  1984,  49:  4214 
  • 14a Tietze LF. Schneider C. J. Org. Chem.  1991,  56:  2476 
  • 14b Kan A. Kang SY. Choi HW. Kim CM. Jun HS. Younb JH. Synthesis  2004,  1102 
  • 15 Carey FA. Sundberg RJ. Advanced Organic Chemistry: Reactions and Synthesis (Part B)   4th ed.:  Plenum; New York: 2002.  p.205 
  • 16 Michael HKC. VanNieuwenhze S. Sharpless KB. Chem. Rev.  1994,  94:  2483 
  • 18 Nakamura E. Inubushi T. Aoki S. Machii D. J. Am. Chem. Soc.  1991,  113:  8980 
13

Compound similar to 9 has been synthesized in different steps. See ref. 5e.

17

These attempts include oxidating 12 with MCPBA, or aerobic oxidation in the presence of Bu3SnH, and hydrolyzation with H2O either in strong polar solvents or in the presence of a base.