Download PDF
Synlett 2002(8): 1326-1328
DOI: 10.1055/s-2002-32987
LETTER
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of Parallel Cyclobolaphiles Having Two Diacetylenes: Mimetics of Archaeal Membrane Lipids

Kazuhiro Miyawaki, Toshiyuki Takagi, Motonari Shibakami*
Institute for Materials and Chemical Process, Institute of Advanced Industrial Science and Technology (AIST), Central 5th, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Fax: +81(298)614698; e-Mail: moto.shibakami@aist.go.jp;
Further Information

Publication History

Received 22 May 2002
Publication Date:
25 July 2002 (online)

    Permissions and Reprints All articles of this category

Abstract

Chiral 48-membered parallel cyclobolaphiles and their diastereomer having two diacetylenes were efficiently synthesized by utilizing both the selective deprotection and the cross-coupling method of two distinct acetylenic compounds.

Key words

archaeal lipid - diacetylene - chirality - parallel cyclo­bolaphile - mimetics

    References

  • 1a Kushwaha SC. Kates M. Sprott GD. Smith ICP. Biochim. Biophys. Acta  1981,  664:  156 
    Google Scholar
  • 1b Comita PB. Gagosian RB. Pang H. Costello CE. J. Biol. Chem.  1984,  254:  15234 
    Google Scholar
  • 1c Eguchi T. Arakawa K. Terachi T. Kakinuma K. J. Org. Chem.  1997,  62:  1924 
    Google Scholar
  • 1d Eguchi T. Ibaragi K. Kakinuma K. J. Org. Chem.  1998,  63:  2689 
    Google Scholar
  • 1e Aoki T. Poulter CD. J. Org. Chem.  1985,  50:  5634 
    Google Scholar
  • 2a Menger FM. Chen XY. Tetrahedron Lett.  1996,  37:  323 
    CrossrefGoogle Scholar
  • 2b Menger FM. Chen XF. Brocchini S. Hopkins HP. Hamilton D. J. Am. Chem. Soc.  1993,  115:  6600 
    CrossrefGoogle Scholar
  • 2c Yamauchi K. Sakamoto Y. Moriya A. Yamada K. Hosokawa T. Higuchi T. Kinoshita M. J. Am. Chem. Soc.  1990,  112:  3188 
    CrossrefGoogle Scholar
  • 2d Moss RA. Li JM. J. Am. Chem. Soc.  1992,  114:  9227 
    CrossrefGoogle Scholar
  • 2e Fuhrhop J.-H. David HH. Mathieu L. Liman U. Winter HJ. Boekema E. J. Am. Chem. Soc.  1986,  108:  1785 
    CrossrefGoogle Scholar
  • 2f Meglio CD. Rananavare SB. Svenson S. Thompson DH. Langmuir  2000,  16:  128 
    CrossrefGoogle Scholar
  • 2g Kim JM. Thompson DH. Langmuir  1992,  8:  637 
    CrossrefGoogle Scholar
  • 2h Ladika M. Fisk TE. Wu WW. Jons SD. J. Am. Chem. Soc.  1994,  116:  12093 
    CrossrefGoogle Scholar
  • 2i Patwarahan AP. Thompson DH. Org. Lett.  1999,  1:  241 
    CrossrefGoogle Scholar
  • 3a Schnur JM. Science  1993,  262:  1669 
    CrossrefGoogle Scholar
  • 3b Spector MS. Price RR. Schnur JM. Adv. Mater.  1999,  11:  337 
    CrossrefGoogle Scholar
  • 3c Schnur JM. Ratna BR. Selinger JV. Singh A. Jyothi G. Easwaran RK. Science  1994,  264:  945 
    CrossrefGoogle Scholar
  • 3d Selinger JV. Schnur JM. Phys. Rev. Lett.  1993,  71:  4091 
    CrossrefGoogle Scholar
  • 3e Spector MS. Selinger JV. Singh A. Rodriguez JM. Price RP. Schnur JM. Langmuir  1998,  14:  3493 
    CrossrefGoogle Scholar
  • 4a Amphiphilic molecules containing a polar head group at the end of a hydrophobic segment have been termed ‘bolaamphiphiles’: Fuhrhop J.-H. Mathiewu J. Angew. Chem., Int. Ed. Engl.  1984,  23:  100 
    CrossrefGoogle Scholar
  • 4b Also termed ‘bolaphile’: Jayasuriya N. Bosak S. Regen SL. J. Am. Chem. Soc.  1990,  112:  5844 
    CrossrefGoogle Scholar
  • 4c

    While amphiphiles having a macrocyclic ring as a hydrophobic segment have been termed ‘macrocyclic bolaamphiphiles’ (see Ref. [2a] ), we prefer to adopt the abbreviated and more readily pronounceable term, ‘cyclobolaphile’.
    Crossref
  • 5a We term caldarchaeol with a parallel arrangement of glycerol units ‘parallel caldarchaeol’, and that with an antiparallel arrangement ‘antiparallel caldarchaeol’: Gräther O. Arigoni D. J. Chem. Soc., Chem. Commun.  1995,  405 
    Google Scholar
  • 5b Nishihara M. Morii H. Koga Y. J. Biochem.  1987,  101:  1007 
    Google Scholar
  • 7 Qin D. Byun H. Bittman R. J. Am. Chem. Soc.  1999,  121:  662 
    CrossrefGoogle Scholar
  • 8 Carvalho JF. Prestwich GD. J. Org. Chem.  1984,  49:  1251 
    CrossrefGoogle Scholar
  • 9 Hirth G. Barner R. Helv. Chim. Acta  1982,  65:  1059 
    CrossrefGoogle Scholar
  • 10 Oikawa Y. Yoshioka T. Yonemitsu O. Tetrahedron Lett.  1982,  23:  885 
    CrossrefGoogle Scholar
  • 12 Hansen WJ. Murari R. Wedmid Y. Baumann WJ. Lipids  1982,  17:  453 
    Google Scholar
  • 13 Alami M. Ferri F. Tetrahedron Lett.  1996,  37:  2763 
    CrossrefGoogle Scholar
6

Intense examination of macrocyclic synthetic methods that have been previously reported indicates that only our strategy has the potential to provide three stereoisomers of parallel cyclobolaphiles that contain diacetylene units (see Ref. [1c] [d] [2] ).

11

All new compounds gave satisfactory analytical and spectral data. Selected physical data are as follows: 4: Stage yellow oil, Rf = 0.55 [hexane/ethyl acetate (2:1, v/v)], [α]D 28 -1.67 (c 0.24, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 7.45-7.39 (m, 12 H), 7.27-7.19 (m, 18 H), 7.16 (d, J = 8.8 Hz, 4 H), 6.81 (d, J = 8.5 Hz, 4 H), 4.44 (d, J = 11.6 Hz, 2 H), 4.40 (d, J = 11.9 Hz, 2 H), 3.77 (s, 6 H), 3.56-3.49 (m, 10 H), 3.17 (d, J = 4.6 Hz, 4 H), 2.19 (t, J = 7.2 Hz, 4 H), 1.56-1.44 (m, 8 H), 1.34-1.24 (m, 16 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 159.06, 144.09, 130.48, 129.13, 128.72, 127.70, 126.87, 113.62, 86.48, 78.29, 77.52, 72.87, 70.60, 70.09, 65.22, 63.44, 55.24, 30.06, 29.33, 29.07, 28.82, 28.32, 26.10, 19.17 ppm. Anal. Calcd for C80H90O8: C, 81.46; H, 7.69%. Found: C, 81.43; H, 7.66%. 8: Stage pale yellow oil, Rf = 0.13 [hexane/ethyl acetate (2:1, v/v)], [α]D 28 -9.80 (c 0.60, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 3.72-3.48 (m, 18 H), 2.23 (t, J = 6.9 Hz, 8 H), 2.17 (brs, 2 H), 1.65-1.42 (m, 16 H), 1.40-1.19 (m, 32 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 78.44, 77.41, 71.60, 71.08, 70.34, 65.31, 62.90, 29.95, 29.46, 29.26, 29.10, 28.93, 28.58, 28.19, 25.93, 19.11 ppm. LRMS (FAB): m/z = 725 [(M + H)+]. Anal. Calcd for C46H76O6: C, 76.20; H, 10.56%. Found: C, 76.19; H, 10.81%. 10: [α]D 28 +9.67 (c 0.30, CHCl3). 15: [α]D 28 0.00 (c 0.45, CHCl3). (2R,27R)-1: Stage pale yellow solid, Rf = 0.1 [CHCl3/MeOH/H2O (65:25:4, v/v/v)]. [α]D 28 +5.81 (c 0.75, MeOH). 1H NMR [500 MHz, CDCl3/CD3OD (97:3, v/v)]: δ = 4.24 (brs, 4 H), 3.84 (t, J = 5.3 Hz, 4 H), 3.65 (brs, 4 H), 3.58-3.51 (m, 8 H), 3.43-3.37 (m, 6 H), 3.24 (s, 18 H), 2.21 (t, J = 6.7 Hz, 8 H), 1.49-1.43 (m, 16 H), 1.34-1.20 (m, 32 H) ppm. 13C NMR (125 MHz, CD3OD):
δ = 79.50, 77.97, 72.46, 72.01, 71.49, 67.47, 66.57, 66.20, 60.37, 54.69, 31.21, 30.78, 30.41, 30.24, 29.98, 29.83, 29.58, 27.29, 19.79 ppm. 31P NMR [200 MHz, CDCl3/CD3OD (99:1, v/v)]: δ = -0.50 (s)ppm. LRMS (FAB): m/z = 1054 (M+), 995 [(M - (Me)3N)+]. Anal. Calcd for C56H100N2O12P2·2 H2O: C, 61.63; H, 9.60; N, 2.57%. Found: C, 61.59; H, 9.43; N, 2.56%. (2S,27S)-1: [α]D 28 -5.77 (c 0.70, MeOH). (2R,27S)-1: [α]D 28 +0.00 (c 0.37, MeOH). The spectral data of (2R,27S)-1 and (2S,27S)-1 were identical with those of (2R,27R)-1.