RESEARCH ARTICLE

 

[H₂-cryptand 222]²⁺(Br₃^-)₂ as a tribromide-type catalyst for the trimethylsilylation/tetrahydropyranylation of alcohols

 

 

Gholamabbas Chehardoli^{I, *}; Mohammad Ali Zolfigol^II; Vahid Khakyzadeh^II; Hadi GholamiK^II; Khodabakhsh Niknam^III

^ISchool of Pharmacy, Hamedan University of Medical Sciences, 65178 Hamedan, Iran
^IIFaculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
^IIIDepartment of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr 75169, Iran

 

 

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ABSTRACT

A stable organic tribromide, [H₂-cryptand 222]²⁺(Br₃-)₂ was utilized as an active catalyst for the trimethylsilylation/ tetrahydropyranylation of alcohols. The method is general for the preparation of OH-protected aliphatic (acyclic and cyclic), aromatic, primary, secondary and tertiary alcohols.

Keywords: [H₂-cryptand 222]²⁺(Br₃-)₂, trimethylsilylation, tetrahydropyranylation, alcohols, tribromide, TMS-ether, THP-ether

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Acknowledgements

This paper was extracted from the M.Sc. thesis of Vahid Khakyzadeh. The authors acknowledge financial support for this work from the research affairs of Hamedan University of Medi-calSciences,Hamedan,I.R. Iranandpartialsupportofthis work by the Research Affairs Office of Bu-Ali Sina University (Grant number 32-1716 entitled development of chemical methods, reagent and molecules.),and also Center ofExcellence inDevelopment of Chemical Method (CEDCM) Hamedan, I.R. Iran.

 

References

1 (a) Z.B. Huang and S.H. Chang, Synlett., 2005, 1703;         [ Links ] (b) Z.B. Huang and S.H. Chang, Synlett., 2005, 2257;         [ Links ] (c) Z.B. Huang, T.J. Kang and S.H. Chang, Tetrahedron Lett., 2005, 46,3461;         [ Links ] (d) Z.B. Huang, S.H. Kim and S.H. Chang,Synlett.,2006,1707;         [ Links ] (e) Z.B. Huangand S.H. Chang, Tetrahedron Lett., 2005, 46, 5351.         [ Links ]

2 (a) L.F. Lindoy, J. Iran. Chem. Soc., 2004, 1, 1;         [ Links ] (b) J. Hua and Y.G. Wang, 2005, Chem. Lett., 34, 1.         [ Links ]

3 C. Muthukumar and S.D. Kesarkar andD.N. Srivastava, J. Electroanal. Chem., 2007, 602, 172.         [ Links ]

4 (a) H.J. Bushmann, G. Wenz, E. Schollmeyer and L. Mutihac, Inorg. Chem. Commun., 2001, 4, 211;         [ Links ] (b) T.M. Letcher, J.D. Mercer-Chalmers and R.L. Kay, Pure & Appl. Chem., 1994, 66, 419;         [ Links ] (c) M. Dhifet, M.S. Belkhiria, J. Daran and H. Nasri, Acta Cryst., 2009, E65, m967.         [ Links ]

5 H.R. Pouretedal and A. Semnani, Iran. J. Chem. Chem. Eng., 2005, 24, 53.         [ Links ]

6 V.J. Mathew and S.M. Khopkar, J. Radioanal. Nucl. Chem. Lett., 1995, 201, 281.         [ Links ]

7 G.Bracke,M.SatirandP.Krau,Clays and Clay Minerals,1995, 43, 732.         [ Links ]

8 M.N. Gandhi and S.M. Khopkar, Mikrochim. Acta, 1993, 111, 93.         [ Links ]

9 (a) F.D. Cattaway and G. Hoyle, J. Chem. Soc., 1923, 654;         [ Links ] (b) M. Avramoff, J. Weiss and O. Schaechter, J. Org. Chem., 1963, 28, 3256.         [ Links ]

10 S. Kajigneshi, T. Kakinami, H. Tokiyama, T. Hirakawa and T. Okamoto,Chem. Lett.,1987, 627.         [ Links ]

11 R.E.Buckles, A.I.Popov, W.F.Zeleznyand R.J.Smith, J.Am.Chem.Soc., 1951, 73, 4525.         [ Links ]

12 H.A. Muathen, J. Org. Chem., 1992, 57, 2740.         [ Links ]

13 L.F. Fieser and M. Fieser, Reagents for Organic Synthesis, Wiley, New York, USA, 1967.         [ Links ]

14 I. Yavari and A. Shaabani,J.Chem.Res.(S), 1994, 7, 274.         [ Links ]

15 M.M. Heravi, F. Derikvand, M. Ghassemzadeh and B. Neumuller, Tetrahedron Lett., 2005, 46, 6243.         [ Links ]

16 W. Bao and Z. Wang,GreenChem., 2006, 8, 1028.         [ Links ]

17 C. Chiappe, E. Leandri and D. Pieraccini, Chem. Commun., 2004, 2536.         [ Links ]

18 M.A. Zolfigol, G. Chehardoli, S. Salehzadeh, H. Adams and M.D. Ward,Tetrahedron Lett.,2007,48, 7969.         [ Links ]

19 (a)M.K.Chaudhuri,A.T.KhanandB.K.Patel,TetrahedronLett.,1998, 39, 8163;         [ Links ] (b) H.Z. Boeini, J. Iran. Chem. Soc., 2009, 6, 547.         [ Links ]

20 T.W. GreenandP.G.M. Wuts,Protective Groups in Organic Synthesis,3rd edn., Wiley, New York, USA, 1999.         [ Links ]

21 (a) W.H. Pinnick, B.S. Bal and N.H. Lajis, Tetrahedron Lett., 1978, 4261;         [ Links ] (b)T.Morita,Y.Okomoto and H.Sakuti,Tetrahedron Lett., 1980, 21,835;         [ Links ] (c) J. Cossy and P. Pale, Tetrahedron Lett., 1978, 6093;         [ Links ] (d) S. Tarkelson and C. Anisworth, Synthesis, 1976, 722.         [ Links ]

22 C.A. Bruynes and T.K. Jurrines, J. Org. Chem., 1982, 47, 3966.         [ Links ]

23 (a) Z.H. Zhang, T.S. Li, F. Yang and C.G. Fu, Synth. Commun., 1998,28, 305;         [ Links ] (b) M. Curini, F. Epifano, M.C. Marcotullio, O. Rosati and U. Constantino, Synth. Commun., 1999, 29, 541;         [ Links ] (c) H. Firouzabadi, N. Iranpoor, K. Amani and F. Nowrouzi, J. Chem. Soc, Perkin Trans. 1, 2002, 2601;         [ Links ] (d) B. Karimi and B. Golshani, J. Org. Chem., 65, 2000, 7228;         [ Links ] (e) A. Khazaei, M.A. Zolfigol, A. Rostami and A.G. Choghamarani, Catal. Commun., 2006, 7, 399;         [ Links ] (f) F. Shirini, M.A. Zolfigol and K. Mohammadi, Phosphorous, Sulfur Silicon Relat. Elem., 2003, 178, 1567;         [ Links ] (g) F. Shirini, M.A. Zolfigol and M. Abedini, Bull. Chem. Soc. Jpn., 2005, 78, 1982;         [ Links ] (h) A. Khazaei, S. Rahmati and A. Rostami, Helv. Chim. Acta, 2009, 92, 1434;         [ Links ] (i) A. Khazaei, M.A. Zolfigol, Z. Tanbakouchian, M. Shiri, K. Niknam and J. Saien, Catal. Commun., 8, 2007, 917;         [ Links ] (j) M. Moghadam, S. Tangestaninejad, V. Mirkhani, I. Mohammadpoor-Baltork, S. Chahardahcheric and Z. Tavakoli, J. Organomet. Chem., 2008, 693, 2041;         [ Links ] (k) M. Mojtahedi, H. Abbasi and M.S. Abaee, J. Mol. Catal. A: Chem., 2006, 250, 6.         [ Links ]

24 T. Mineno, Tetrahedron Lett, 43, 2002, 7975.         [ Links ]

25 (a) R.G. Jones and M.J. Mann, J. Am. Chem. Soc, 1953, 75, 4048;         [ Links ] (b) M. Miyashita, A. Yoshikoshi and P.A. Grieco, J. Org. Chem., 1977, 42, 3772;         [ Links ] (c) Y. Ogawa and M. Shibasaki, Tetrahedron Lett., 1984, 25, 663;         [ Links ] (d) V.V. Namboodiri and R.S. Varma, Tetrahedron Lett., 2002, 43, 1143;         [ Links ] (e) N. Ravindranath, C. Ramesh and B. Das, Synlett, 2001, 1777;         [ Links ] (f) N. Rezai, F.A. Meybodi and P. Salehi, Synth. Commun., 2000, 30, 1799;         [ Links ] (g) B. Karimi and M. Khalkhali, J. Mol. Catal. A: Chem., 2005, 232, 113;         [ Links ] (h) Y. Wang, X. Wu and Z. Jiang, Tetrahedron Lett., 2004, 45, 2973;         [ Links ] (i) M.M. Heravi, F.K. Behbahani, H.A. Oskooie and R.H. Shoar, TetrahedronLett., 2005, 46, 2543;         [ Links ] (j) S. Naik, R. Gopinath andB.K. Patel, Tetrahedron Lett., 2001, 42, 7679;         [ Links ] (k) A. Khazaei, A. Rostami and M. Mahboubifar, Catal. Commun., 2007, 8, 383.         [ Links ]

26 (a) M.A. Zolfigol, M.H. Zebarjadian, G. Chehardoli, H. Keypour, S. Salehzadeh and M. Shamsipur, J. Org. Chem., 2001, 66, 3619;         [ Links ] (b) M.A. Zolfigol, M.H. Zebarjadian, G. Chehardoli, S.E. Mallakpour and M. Shamsipur, Tetrahedron, 2001, 57, 1627;         [ Links ] (c) K. Niknam and M.A. Zolfigol, J. Iran. Chem. Soc., 2006, 3, 59.         [ Links ]

27 (a) M.A. Zolfigol, G. Chehardoli, E. Ghaemi, E. Madrakian, R. Zare, T. Azadbakht, K. Niknam and S. Mallakpour, Monatsh. Chem., 2008 139, 261;         [ Links ] (b) M.A. Zolfigola, E. Kolvari, N. Koukabi, S. Salehzadeh, G. Chehardoli, I.S. Tidmarsh and K. Niknam, J. Iran. Chem. Soc., 2011, 8, 484;         [ Links ] (c) G. Chehardoli, M.A. Zolfigol, V. Khakyzadeh, R. Golbedaghi, N.A. Hall and A.G. Blackman, J. Chin. Chem. Soc., 2011, 58, in press.         [ Links ]

28 (a) R. Ghorbani-Vaghei, M.A. Zolfigol, M. Chegeny and H. Veisi, Tetrahedron Lett., 2006, 47, 4505;         [ Links ] (b) K. Niknam, M.A. Zolfigol, G. Chehardoli and M. Dehghanian, Chin. J. Catal., 2008, 29, 901;         [ Links ] (c) M.A. Zolfigol, G. Chehardoli, M. Dehghanian, K. Niknam, F. Shirini and A. Khoramabadi-Zad, J. Chin. Chem. Soc., 2008, 55, 885;         [ Links ] (d) K. Niknam, M.A. Zolfigol, D. Saberi and M. Khonbazi, Chin. J. Chem., 2009, 27, 1548;         [ Links ] (e) F. Shirini, M.A. Zolfigol and M. Abedini, Monatsh. Chem., 2009, 140, 61.         [ Links ]

29 The room-temperature crystal structure of [H₂-cryptand 222]²⁺(Br₃^-)₂ has recently been reported. See A.N. Chekhlov, J. Struct. Chem., 2007, 48, 137.         [ Links ]

 

 

Received 16 May 2011
Revised 8 July 2011
Accepted 21 July 2011

 

 

* To who correspondence should be addressed. E-mail: chehardoli@umsha.ac.ir; cheh1002@gmail.com