Synthesis 2014; 46(14): 1908-1916
DOI: 10.1055/s-0033-1339126
special topic
© Georg Thieme Verlag Stuttgart · New York

Unified Synthesis of (–)-Folicanthine and (–)-Ditryptophenaline Enabled by a Room Temperature Nickel-Mediated Reductive Dimerization

Long Luo
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China   Fax: +86(931)8912586   Email: pengyu@lzu.edu.cn
,
Jian-Jian Zhang
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China   Fax: +86(931)8912586   Email: pengyu@lzu.edu.cn
,
Wei-Jian Ling
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China   Fax: +86(931)8912586   Email: pengyu@lzu.edu.cn
,
Yong-Liang Shao
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China   Fax: +86(931)8912586   Email: pengyu@lzu.edu.cn
,
Ya-Wen Wang
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China   Fax: +86(931)8912586   Email: pengyu@lzu.edu.cn
,
Yu Peng*
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China   Fax: +86(931)8912586   Email: pengyu@lzu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 17 March 2014

Accepted after revision: 05 May 2014

Publication Date:
21 May 2014 (online)

Abstract

A Ni·Phen-mediated reductive homocoupling of an optically active tertiary bromide has been efficiently achieved after the systematic screen of reaction conditions including ligands. This key step establishes sterically hindered vicinal quaternary stereocenters embedded in natural bispyrrolo[2,3-b]indoline alkaloids, thus enabling to realize the first asymmetric total synthesis of (–)-folicanthine via the detailed investigation of a challenging double decarboxylation. Notably, the concise synthesis of diketopiperazine alkaloid (–)-ditryptophenaline was also completed from the common dimeric intermediate.

Supporting Information

 
  • References

    • 1a Everson D, Shrestha R, Weix DJ. J. Am. Chem. Soc. 2010; 132: 920
    • 1b Everson D, Jones BA, Weix DJ. J. Am. Chem. Soc. 2012; 134: 6146
    • 1c Wotal AC, Weix DJ. Org. Lett. 2012; 14: 1476
    • 1d Anka-Lufford LL, Prinsell MR, Weix DJ. J. Org. Chem. 2012; 77: 9989
    • 1e Biswas S, Weix DJ. J. Am. Chem. Soc. 2013; 135: 16192
    • 2a Yu X, Yang T, Wang S, Xu H, Gong H. Org. Lett. 2011; 13: 2138
    • 2b Wu F, Lu W, Qian Q, Ren Q, Gong H. Org. Lett. 2012; 14: 3044
    • 2c Yin H, Zhao C, You H, Lin K, Gong H. Chem. Commun. 2012; 48: 7034
    • 2d Wang S, Qian Q, Gong H. Org. Lett. 2012; 14: 3352
    • 2e Dai Y, Wu F, Zang Z, You H, Gong H. Chem. Eur. J. 2012; 18: 808
    • 2f Xu H, Zhao C, Qian Q, Deng W, Gong H. Chem. Sci. 2013; 4: 4022
  • 3 Cherney AH, Kadunce NT, Reisman SE. J. Am. Chem. Soc. 2013; 135: 7442
    • 4a León T, Correa A, Martin R. J. Am. Chem. Soc. 2013; 135: 1221
    • 4b Correa A, León T, Martin R. J. Am. Chem. Soc. 2014; 136: 1062
    • 5a Yan C.-S, Peng Y, Xu X.-B, Wang Y.-W. Chem. Eur. J. 2012; 18: 6039
    • 5b Xu X.-B, Liu J, Zhang J.-J, Wang Y.-W, Peng Y. Org. Lett. 2013; 15: 550
    • 5c Peng Y, Xu X.-B, Xiao J, Wang Y.-W. Chem. Commun. 2014; 50: 472
    • 6a Peng Y, Luo L, Yan C.-S, Zhang J.-J, Wang Y.-W. J. Org. Chem. 2013; 78: 10960 ; and references cited therein
    • 6b After the acceptance of our article, a related Ni/dppBz-catalyzed dimerization for the syntheses of (±)-folicanthine and (±)-chimonanthine appeared, see: Wada M, Murata T, Oikawa H, Oguri H. Org. Biomol. Chem. 2014; 12: 298
  • 7 For the formal synthesis of (–)-folicanthine employing Pd-DAAA, see: Trost BM, Osipov M. Angew. Chem. Int. Ed. 2013; 52: 9176

    • For the total synthesis of (+)-folicanthine, see:
    • 8a Movassaghi M, Schmidt MA. Angew. Chem. Int. Ed. 2007; 46: 3725
    • 8b Guo C, Song J, Huang J.-Z, Chen P.-H, Luo S.-W, Gong L.-Z. Angew. Chem. Int. Ed. 2012; 51: 1046
    • 8c Mitsunuma H, Shibasaki M, Kanai M, Matsunaga S. Angew. Chem. Int. Ed. 2012; 51: 5217

    • For the total synthesis of (+)-chimonanthine, see refs. 8a,c and:
    • 8d Overman LE, Larrow JF, Stearns BA, Vance JM. Angew. Chem. Int. Ed. 2000; 39: 213

    • For the total synthesis of (–)-chimonanthine, see:
    • 8e Overman LE, Paone D V, Stearns BA. J. Am. Chem. Soc. 1999; 121: 7702
    • 8f Xie W, Jiang G, Liu H, Hu J, Pan X, Zhang H, Wan X, Lai Y, Ma D. Angew. Chem. Int. Ed. 2013; 52: 12924
    • 9a Steven A, Overman LE. Angew. Chem. Int. Ed. 2007; 46: 5488
    • 9b Schmidt MA, Movassaghi M. Synlett 2008; 313
    • 10a Anthoni U, Christophersen C, Nielsen PH In Alkaloids: Chemical and Biological Perspectives . Vol. 13. Pelletier SW. Pergamon; London: 1999: 163-236
    • 10b Tadano S, Ishikawa H. Synlett 2014; 25: 157
    • 10c For a review for the construction of DKP, see: Borthwick AD. Chem. Rev. 2012; 112: 3641
  • 11 López CS, Pérez-Balado C, Rodríguez-Graña P, de Lera ÁR. Org. Lett. 2008; 10: 77

    • For recent reviews on the construction of pyrroloindolines, see:
    • 12a Crich D, Banerjee A. Acc. Chem. Res. 2007; 40: 151
    • 12b Zhang D, Song H, Qin Y. Acc. Chem. Res. 2011; 44: 447
    • 12c Ruiz-Sanchis P, Savina SA, Albericio F, Álvarez M. Chem. Eur. J. 2011; 17: 1388
    • 12d Repka LM, Reisman SE. J. Org. Chem. 2013; 78: 12314
    • 13a Goldup SM, Leigh DA, McBurney RT, McGonigal PR, Plant A. Chem. Sci. 2010; 1: 383
    • 13b Prinsell MR, Everson DA, Weix DJ. Chem. Commun. 2010; 46: 5743
  • 14 For the utilization of this kind of ligands in the nickel-catalyzed conjugate addition of aryl iodides to enones, see ref. 1b and: Shrestha R, Dorn SC. M, Weix DJ. J. Am. Chem. Soc. 2013; 135: 751
  • 15 We also prepared the analogous precursor bearing benzyloxycarbonyl at C2, and found that only 20% of (–)-2 was detected along with 60% of (+)-5 under identical conditions.
  • 16 Depew KM, Marsden SP, Zatorska D, Zatorski A, Bornmann WG, Danishefsky SJ. J. Am. Chem. Soc. 1999; 121: 11953
  • 17 CCDC-990779 [(–)-2] and CCDC-990780 [(–)-3] contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • 18a Springer JP, Büchi G, Kobbe B, Demain AL, Clardy J. Tetrahedron Lett. 1977; 18: 2403
    • 18b Nakagawa M, Sugumi H, Kodato S, Hino T. Tetrahedron Lett. 1981; 22: 5323
    • 18c Maes CM, Potgieter M, Steyn PS. J. Chem. Soc., Perkin Trans. 1 1986; 861
    • 18d Barrow CJ, Cai P, Snyder JK, Sedlock DM, Sun HH, Cooper R. J. Org. Chem. 1993; 58: 6016
    • 19a Overman LE, Paone DV. J. Am. Chem. Soc. 2001; 123: 9465
    • 19b Movassaghi M, Schmidt MA, Ashenhurst JA. Angew. Chem. Int. Ed. 2008; 47: 1485
    • 19c Tadano S, Mukaeda Y, Ishikawa H. Angew. Chem. Int. Ed. 2013; 52: 7990
    • 20a Eiter K, Svierak O. Monatsh. Chem. 1951; 82: 186
    • 20b Eiter K, Svierak O. Monatsh. Chem. 1952; 83: 1453
    • 20c Hodson HF, Smith GF. J. Chem. Soc. 1957; 1877
  • 21 For the concern about this challenging step, see the footnote on page 3725 in ref. 8a.
    • 22a Barton DH. R, Crich D, Motherwell WB. J. Chem. Soc., Chem. Commun. 1983; 939
    • 22b Barton DH. R, Crich D, Motherwell WB. Tetrahedron 1985; 41: 3901
  • 23 Ballestri M, Chatgilialoglu C, Cardi N, Sommazzi A. Tetrahedron Lett. 1992; 33: 1787
    • 24a Foo K, Newhouse K, Mori I, Takayama H, Baran PS. Angew. Chem. Int. Ed. 2011; 50: 2716
    • 24b See also: Martin SF, Clark CW, Corbett JW. J. Org. Chem. 1995; 60: 3236
  • 25 For the recent utilization of this reagent in a related mono-decarboxylation reaction, see: Lathrop SP, Movassaghi M. Chem. Sci. 2014; 5: 333
  • 26 Zhang Y.-A, Liu Q, Wang C, Jia Y. Org. Lett. 2013; 15: 3662
  • 27 Espejo VR, Rainier JD. J. Am. Chem. Soc. 2008; 130: 12894
  • 28 Ghosh AK, Xu X. Org. Lett. 2004; 6: 2055
  • 29 Prepared by neutralization of the corresponding sodium salt with aq 1 M HCl, see: Zhong P, Guo S.-r, Song C.-s. Synth. Commun. 2004; 34: 247