Citation: Jun Yu, Biao Yu. Synthesis of the ABC skeleton of the aglycon of Echinoside A[J]. Chinese Chemical Letters, ;2015, 26(11): 1331-1335. doi: 10.1016/j.cclet.2015.08.010 shu

Synthesis of the ABC skeleton of the aglycon of Echinoside A

  • Corresponding author: Jun Yu,  Biao Yu, 
  • Received Date: 7 July 2015
    Available Online: 3 August 2015

  • Echinoside A is a triterpene saponin isolated from the sea cucumber Actinopyga echinites (JAEGER), which displays potent antitumor activities in vitro and in vivo. Here, we report the synthesis of the ABC-fused ring skeleton of the aglycon of Echinoside A, with the enantiomerically pure (+)-Wieland-Miescher ketone being used as starting material and a Robinson annulation as the key reaction.
  • 加载中
    1. [1]

      [1] (a) I. Kitagawa, T. Inamoto, M. Fuchida, et al., Structures of echinoside A and B, two antifugal oligoglycosides from the sea cucumber Actinopyga echinites (JAEGER), Chem. Pharm. Bull. 28 (1980) 1651-1653; (b) I. Kitagawa, M. Kobayashi, T. Inamoto, et al., Marine natural products. XIV. Structures of echinosides A and B, antifungal lanostane-oligosides from the sea cucumber Actinopyga echinites (JAEGER), Chem. Pharm. Bull. 33 (1985) 5214-5224; (c) M. Kobayashi, M. Hori, K. Kan, et al., Marine natural products. XXVII. Distribution of lanostane-type triterpene oligoglycosides in ten kinds of Okinawan sea cucumbers, Chem. Pharm. Bull. 39 (1991) 2282-2287.

    2. [2]

      [2] M. Li, Z.H. Miao, Z. Chen, et al., Echinoside A, a new marine-derived anticancer saponin, targets topoisomerase2a by unique interference with its DNA binding and catalytic cycle, Ann. Oncol. 21 (2010) 597-607.

    3. [3]

      [3] (a) Y. Yang, S. Laval, B. Yu, Chemical synthesis of saponins, Adv. Carbohydr. Chem. Biol. 37 (2014) 137-226; (b) B. Yu, J. Sun, Current synthesis of triterpene saponins, Chem. Asian J. 4 (2009) 642-654.

    4. [4]

      [4] A. Bañó n-Caballero, G. Guillena, C. Ná jera, et al., Recoverable silica-gel supported binam-prolinamides as organocatalysts for the enantioselective solvent-free intra- and inter-molecular aldol reaction, Tetrahedron 69 (2013) 1307-1315.

    5. [5]

      [5] A. Ali, C.F. Thompson, J.M. Balkovec, et al., Novel N-arylpyrazolo [3,2-c]-based ligands for the glucocorticoid receptor: receptor binding and in vivo activity, J. Med. Chem. 47 (2004) 2441-2452.

    6. [6]

      [6] A.B. Smith, L. Kü rti, A.H. Davulcu, Y.S. Cho, Development of a scalable synthesis of a common eastern tricyclic lactone for construction of the nodulisporic acids, Org. Process Res. Dev. 11 (2007) 19-24.

    7. [7]

      [7] H. Hisahiro, U. Hisashi, Optically pure (4aS)-(+)- or (4aR)-(-)-1,4a-dimethyl-4,4a, 7,8-tetrahydronaphthalene-2,5(3H,6H)-dione and its use in the synthesis of an inhibitor of steroid biosynthesis, J. Org. Chem. 53 (1988) 2308-2311.

    8. [8]

      [8] (a) U. Eder, G. Sauer, R. Wiechert, New type of asymmetric cyclization to optically active steroid CD partial structures, Angew. Chem. Int. Ed. 10 (1971) 496-497; (b) P. Buchschacher, A. Fü rst, J. Gutzwiller, (S)-8a-Methyl-3,4,8,8a-tetrahydro-1,6 (2H, 7H)-naphthalenedione, Org. Synth. 63 (1985) 37.

    9. [9]

      [9] (a) B. Bradshaw, E. Gorka, J. Bonjoch, et al., Efficient solvent-free Robinson annulation protocols for the highly enantioselective synthesis of the Wieland- Miescher ketone and analogues, Adv. Synth. Catal. 351 (2009) 2482; (b) G. Gabriela, N. Carmen, F.V. Santiago, N-Tosyl-(Sa)-binam-L-prolinamide as highly efficient bifunctional organocatalyst for the general enantioselective solvent- free Aldol reaction, Synlett 19 (2008) 3031.

    10. [10]

      [10] D.N. Kirk, V. Petrow, Modified steroid hormones. Part XXVII. A new route to 4-methyl-3-oxo-Δ4-steroids, J. Chem. Soc. (1962) 1091.

    11. [11]

      [11] P. Alexander, S. Karlheinz, Enantioselective total synthesis of (+)-labd-8(17)-ene- 3b, 15-diol and (-)-labd-8(17)-ene-3b,7a,15-triol, Tetrahedron Lett. 38 (1997) 2081-2084.

    12. [12]

      [12] T.A. Spencer, R.A.J. Smith, D.L. Storm, R.M. Villarica, Total synthesis of (+-)-methyl vinhaticoate and (+)-methyl vouacapenate, J. Am. Chem. Soc. 93 (1971) 4856-4864.

    13. [13]

      [13] A. Yajima, K. Mori, Diterpenoid total synthesis, XXXII synthesis and absolute configuration of (-)-phytocassane D, a diterpene phytoalexin isolated from the rice plant, Oryza sativa, Eur. J. Org. Chem. 65 (2000) 4079-4091.

    14. [14]

      [14] K. Ravindar, P.Y. Caron, P. Deslongchamps, Total synthesis of (+)-cassaine utilizing an anionic polycyclization strategy, Org. Lett. 15 (2013) 6270-6273.

  • 加载中

Metrics
  • PDF Downloads(0)
  • Abstract views(650)
  • HTML views(4)

通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索
Address:Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888
Powered By info@rhhz.net

/

DownLoad:  Full-Size Img  PowerPoint
Return