PDF herunterladen
Synthesis 2014; 46(06): 787-798
DOI: 10.1055/s-0033-1338583
paper
© Georg Thieme Verlag Stuttgart · New York

Efficient Preparation of Apically Substituted Diamondoid Derivatives

Paul Kahl
a   Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   eMail: prs@uni-giessen.de
,
Boryslav A. Tkachenko
a   Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   eMail: prs@uni-giessen.de
,
Anatoliy A. Novikovsky
b   Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev, Ukraine    eMail: aaf@xtf.ntu-kpi.kiev.ua
,
Jonathan Becker
c   Institute of Inorganic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany
,
Jeremy E. P. Dahl
d   Stanford University, Stanford Institute for Materials & Energy Science, 476 Lomita Mall, Stanford, CA 94305, USA
,
Robert M. K. Carlson
d   Stanford University, Stanford Institute for Materials & Energy Science, 476 Lomita Mall, Stanford, CA 94305, USA
,
Andrey A. Fokin*
a   Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   eMail: prs@uni-giessen.de
b   Department of Organic Chemistry, Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev, Ukraine    eMail: aaf@xtf.ntu-kpi.kiev.ua
,
Peter R. Schreiner*
a   Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   eMail: prs@uni-giessen.de
› Institutsangaben
Weitere Informationen

Publikationsverlauf

Received: 30. November 2013

Accepted: 13. Dezember 2013

Publikationsdatum:
10. Januar 2014 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik


Abstract

We present an effective three-step chromatography-free sequence for the preparation of apical monohydroxy derivatives of diamantane, triamantane, and [121]tetramantane from the corresponding bis-apical diols utilizing tert-butyldimethylsilyl chloride as the monosilylating agent. The procedure was successfully applied to the monoprotection of several other aliphatic and aromatic diols. Additionally, 9-aminodiamantan-4-carboxylic acid, which has significant potential in medicinal and material sciences, was prepared through Ritter reaction of 4,9-dihydroxydiamantane in trifluoroacetic acid.

Key words

amino acids - diols - monoprotection - nanostructures - silyl protecting groups

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
  • Supporting Information
 

  • References

  • 1 Performed X-ray crystal structure analyses.
    • 2a Hala S, Landa S, Hanus V. Angew. Chem., Int. Ed. Engl. 1966; 5: 1045
      Crossref
    • 2b Lin R, Wilk ZA. Fuel 1995; 74: 1512
      Crossref
    • 2c Dahl JE. P, Moldowan JM, Peakman TM, Clardy JC, Lobkovsky E, Olmstead MM, May PW, Davis TJ, Steeds JW, Peters KE, Pepper A, Ekuan A, Carlson RM. K. Angew. Chem. Int. Ed. 2003; 42: 2040
      Crossref
    • 2d Dahl JE, Liu SG, Carlson RM. K. Science 2003; 299: 96
      CrossrefPubMed
  • 3 Wanka L, Iqbal K, Schreiner PR. Chem. Rev. 2013; 113: 3516
    Crossref
    • 4a Ishiwata H, Acremann Y, Scholl A, Rotenberg E, Hellwig O, Dobisz E, Doran A, Tkachenko BA, Fokin AA, Schreiner PR, Dahl JE. P, Carlson RM. K, Melosh N, Shen Z.-X, Ohldag H. Appl. Phys. Lett. 2012; 101: 163101
      Crossref
    • 4b Zhang J, Zhu Z, Feng Y, Ishiwata H, Miyata Y, Kitaura R, Dahl JE. P, Carlson RM. K, Fokina NA, Schreiner PR, Tománek D, Shinohara H. Angew. Chem. Int. Ed. 2013; 52: 3717
      Crossref
    • 5a Yang WL, Fabbri JD, Willey TM, Lee JR. I, Dahl JE, Carlson RM. K, Schreiner PR, Fokin AA, Tkachenko BA, Fokina NA, Meevasana W, Mannella N, Tanaka K, Zhou XJ, van Buuren T, Kelly MA, Hussain Z, Melosh NA, Shen ZX. Science 2007; 316: 1460
      CrossrefPubMed
    • 5b Clay WA, Liu Z, Yang WL, Fabbri JD, Dahl JE, Carlson RM. K, Sun Y, Schreiner PR, Fokin AA, Tkachenko BA, Fokina NA, Pianetta PA, Melosh N, Shen ZX. Nano Lett. 2009; 9: 57
      Crossref
    • 5c Zhang WH, Gao B, Yang JL, Wu ZY, Carravetta V, Luo Y. J. Chem. Phys. 2009; 130: 54705
      Crossref
    • 5d Roth S, Leuenberger D, Osterwalder J, Dahl JE, Carlson RM. K, Tkachenko BA, Fokin AA, Schreiner PR, Hengsberger M. Chem. Phys. Lett. 2010; 495: 102
      Crossref
  • 6 Hohman JN, Claridge SA, Kim M, Weiss PS. Mater. Sci. Eng. R: Rep. 2010; 70: 188
    Crossref
    • 7a Willey TM, Fabbri JD, Lee JR. I, Schreiner PR, Fokin AA, Tkachenko BA, Fokina NA, Dahl JE. P, Carlson RM. K, Vance AL, Yang WL, Terminello LJ, van Buuren T, Melosh NA. J. Am. Chem. Soc. 2008; 130: 10536
      CrossrefPubMed
    • 7b Willey TM, Lee JR. I, Fabbri JD, Wang D, Nielsen MH, Randel JC, Schreiner PR, Fokin AA, Tkachenko BA, Fokina NA, Dahl JE. P, Carlson RM. K, Terminello LJ, Melosh NA, van Buuren T. J. Electron Spectrosc. Relat. Phenom. 2009; 172: 69
      Crossref
  • 8 Schwertfeger H, Fokin AA, Schreiner PR. Angew. Chem. Int. Ed. 2008; 47: 1022
    CrossrefPubMed
  • 9 Fokin AA, Tkachenko BA, Gunchenko PA, Gusev DV, Schreiner PR. Chem. Eur. J. 2005; 11: 7091
    CrossrefPubMed
  • 10 Schreiner PR, Fokina NA, Tkachenko BA, Hausmann H, Serafin M, Dahl JE. P, Liu SG, Carlson RM. K, Fokin AA. J. Org. Chem. 2006; 71: 6709
    CrossrefPubMed
  • 11 Fokin AA, Gunchenko PA, Novikovsky AA, Shubina TE, Chernyaev BV, Dahl JE. P, Carlson RM. K, Yurchenko AG, Schreiner PR. Eur. J. Org. Chem. 2009; 5153
    • 12a Schwertfeger H, Wuertele C, Serafin M, Hausmann H, Carlson RM. K, Dahl JE. P, Schreiner PR. J. Org. Chem. 2008; 73: 7789
      CrossrefPubMed
    • 12b Schwertfeger H, Wuertele C, Hausmann H, Dahl JE. P, Carlson RM. K, Fokin AA, Schreiner PR. Adv. Synth. Catal. 2009; 351: 1041
      Crossref
  • 13 Fokina NA, Tkachenko BA, Merz A, Serafin M, Dahl JE. P, Carlson RM. K, Fokin AA, Schreiner PR. Eur. J. Org. Chem. 2007; 4738
  • 14 Greene TW, Wuts PG. M. Protective Groups in Organic Synthesis . Wiley; New York: 1999. 3rd ed.
    CrossrefGoogle Scholar
    • 16a Bartoszewicz A, Kalek M, Stawinski J. Tetrahedron 2008; 64: 8843
      Crossref
    • 16b Bartoszewicz A, Kalek M, Nilsson J, Hiresova R, Stawinski J. Synlett 2008; 37
      Artikel in Thieme Connect
  • 17 Isolation can be performed utilizing column chromatography. In this case, yields of the respective mono- and disilylated diamondoid derivatives are the following: from 4: 1.044 g (78%) of 10, 0.138 g (8%) of 11; from 5: 1.025 g (66%) of 15, 0.569 g (28%) of 16; from 6: 1.325 g (76%) of 17, 0.416 g (19%) of 18. 4,9-Bis(tert-butyldimethylsiloxy)diamantane (11): colorless solid; mp 171–172 °C. 1H NMR (400 MHz, CDCl3): δ = 1.85 (s, 6 H), 1.72 (s, 12 H), 0.85 (s, 18 H), 0.06 (s, 12 H). 13C NMR (100 MHz, CDCl3): δ = 69.66 (C), 45.37 (CH2), 38.99 (CH), 25.80 (CH3), 17.93 (C), –1.72 (CH3). MS: m/z (%) = 433 (2), 391 (100), 317 (98), 260 (1), 209 (2), 186 (5), 167 (45), 149 (4), 131 (8), 91 (11), 75 (23), 73 (54), 59 (4). HRMS: m/z calcd for C26H48O2Si2: 448.3193; found: 448.3184.
  • 18 Schwertfeger H, Machuy MM, Wurtele C, Dahl JE. P, Carlson RM. K, Schreiner PR. Adv. Synth. Catal. 2010; 352: 609
    Crossref
  • 19 Tkachenko BA, Fokina NA, Chernish LV, Dahl JE. P, Liu SG, Carlson RM. K, Fokin AA, Schreiner PR. Org. Lett. 2006; 8: 1767
    CrossrefPubMed
  • 20 Fokin AA, Butova ED, Chernish LV, Fokina NA, Dahl JE. P, Carlson RM. K, Schreiner PR. Org. Lett. 2007; 9: 2541
    CrossrefPubMed
  • 21 Fokina NA, Tkachenko BA, Dahl JE. P, Carlson RM. K, Fokin AA, Schreiner PR. Synthesis 2012; 44: 259
    Artikel in Thieme Connect
    • 22a Wanka L, Cabrele C, Vanejews M, Schreiner PR. Eur. J. Org. Chem. 2007; 1474
    • 22b Ranganathan D, Haridas V, Madhusudanan KP, Roy R, Nagaraj R, John GB, Sukhaswami MB. Angew. Chem., Int. Ed. Engl. 1996; 35: 1105
      Crossref
    • 22c Tsuzuki N, Hama T, Hibi T, Konishi R, Futaki S, Kitagawa K. Biochem. Pharmacol. 1991; 41: R5
      Crossref
    • 22d Ranganathan D, Kurur S. Tetrahedron Lett. 1997; 38: 1265
      Crossref
    • 22e Ranganathan D, Haridas V, Madhusudanan KP, Roy R, Nagaraj R, John GB. J. Am. Chem. Soc. 1997; 119: 11578
      Crossref
    • 22f Kuroda Y, Ueda H, Nozawa H, Ogoshi H. Tetrahedron Lett. 1997; 38: 7901
      Crossref
  • 23 Lysenko AB, Senchyk GA, Lincke J, Lassig D, Fokin AA, Butova ED, Schreiner PR, Krautscheid H, Domasevitch KV. Dalton Trans. 2010; 39: 4223
    Crossref
    • 24a Kovalev V, Khomich E, Shokova E, Luzikov Y. ARKIVOC 2008; (iv): 26
    • 24b Maurin JK, Lasek W, Gorska A, Switaj T, Jakubowska AB, Kazimierezuk Z. Chem. Biodivers. 2004; 1: 1498
      Crossref
  • 25 Jirgensons A, Kauss V, Kalvinsh I, Gold MR. Synthesis 2000; 1709
    Artikel in Thieme Connect
    • 26a Courtney T, Johnston DE, McKervey MA, Rooney JJ. J. Chem. Soc., Perkin Trans. 1 1972; 2691
      Crossref
    • 26b Duddeck H, Hollowood F, Karim A, McKervey MA. J. Chem. Soc., Perkin Trans. 2 1979; 360