Synthesis 2010(11): 1891-1898  
DOI: 10.1055/s-0029-1218753
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Cyclodehydration of Fluorinated Diols Using the Mitsunobu Reaction: Highly Efficient Synthesis of Trifluoromethylated Cyclic Ethers

G. K. Surya Prakash*, Clement Do, Fang Wang, Thomas Mathew, George A. Olah*
Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA 90089-1661, USA
e-Mail: gprakash@usc.edu;
Further Information

Publication History

Received 5 March 2010
Publication Date:
23 April 2010 (eFirst)

Abstract

Synthesis of trifluoromethylated cyclic ethers has been achieved via the Mitsunobu cyclodehydration of fluorinated diols with high efficacy. The methodology is found to be widely applicable to the synthesis of cyclic ethers with varying ring size (3-7) from fluorinated diols of differing acidities and steric demands. Cyclic ethers with considerable ring strain can be achieved in moderate yields by this protocol. The methodology is suitable for both primary and secondary alcohols as well as benzylic and aliphatic alcohols as electrophiles to afford the corresponding products in moderate to good yields.

    References

  • 1a Zurer PS. Chem. Eng. News  1993,  (Nov. 15):  12 
  • 1b Lamanna WM, Flynn RM, Vitcak DR, and Qiu Z.-M. inventors; PCT Int. Appl., WO  9947480.  1999; Chem. Abstr. 1999, 131, 230275
  • 2a Takata N, Mochizuki T, Fujimoto E, and Sekiya A. inventors; Japanese Patent  10045651.  1998; Chem. Abstr. 1998, 128, 192366
  • 2b Dams RJ, Qiu Z.-M, Smolders RL, Coppens DM, and Nagase M. inventors; PCT Int. Appl., WO  9916809.  1999; Chem. Abstr. 1999, 130, 282529
  • 3a McClinton MA. McClinton DA. Tetrahedron  1992,  48:  6555 
  • 3b Becker A. Inventory of Industrial Fluoro-Biochemicals   Eyrolles; Paris: 1996. 
  • 4 Dmowski W. Kaminski M. J. Fluorine Chem.  1983,  23:  207 
  • 5a Feiring AF. J. Org. Chem.  1979,  44:  2907 
  • 5b Langlois B. Desbois M. Ann. Chim. (Paris)  1984,  9:  729 
  • 5c Salom J. Mauger C. Brunet S. Schanen V.
    J. Fluorine Chem.  2004,  125:  1947 
  • 6 Ben-David I. Rechavi D. Mishani E. Rozen S.
    J. Fluorine Chem.  1999,  97:  75 
  • 7 Christe KO. Hegge J. Hoge B. Haiges R. Angew. Chem. Int. Ed.  2007,  46:  6155 
  • 8 Prakash GKS. Hu J. Olah GA. ARKIVOC  2003,  (iii):  104 
  • 9a Koller R. Stanek K. Stolz D. Aardoom R. Niedermann K. Togni A. Angew. Chem. Int. Ed.  2009,  48:  4332 
  • 9b Umemoto T. Adachi K. Ishihara S. J. Org. Chem.  2007,  72:  6905 
  • 9c Prakash GKS. Ledneczki I. Chacko S. Olah GA. Org. Lett.  2008,  10:  557 
  • 9d Prakash GKS. Weber C. Chacko S. Olah GA. Org. Lett.  2007,  9:  1863 
  • 9e For a recent review, see: Manteau B. Pazenok S. Vors J.-P. Leroux FR.
    J. Fluorine Chem.  2010,  131:  140 
  • 10 Marrec O. Billard T. Vors J.-P. Pazenok S. Langlois BR. J. Fluorine Chem.  2010,  131:  200 
  • 11 Satake K. inventors; PCT Int. Appl. WO  9925714.  1999; Chem. Abstr. 1999, 131, 5190
  • 12 Eger EI. Leman D. Laster MJ. Liao M. Jankowska K. Raghavanpillai A. Popov AV. Gan Y. Lou Y. Anesth. Analg.  2007,  104:  1090 
  • 13 Leroux F. Jeschke P. Schlosser M. Chem. Rev.  2005,  105:  827 
  • 14 Shishido Y. Wakabayashi H. Koike H. Ueno N. Nukui S. Yamagishi T. Murata Y. Naganeo F. Mizutani M. Shimada K. Fujiwara Y. Sakakibara A. Suga O. Kusano R. Ueda S. Kanai Y. Tsuchiya M. Satake K. Bioorg. Med. Chem.  2008,  16:  7193 
  • 15 Becker H.-D. J. Org. Chem.  1970,  35:  2099 
  • 16 Parham WE. Sayed YA. Synthesis  1976,  116 
  • 17 Swamy KCK. Kumar NNB. Balaraman E. Kumar KVPP. Chem. Rev.  2009,  109:  2551 
  • 18 Falck JR. Yu J. Cho H.-S. Tetrahedron Lett.  1994,  35:  5997 
  • 19 Obach RS, and Scully DA. inventors; PCT Int. Appl. WO  0071538.  2000; Chem. Abstr. 2001, 134, 17405
  • 20 Caron S, and Vazquez E. inventors; Eur. Pat. Appl. EP  1095939A2.  2001; Chem. Abstr. 2001, 134, 326407
  • 21a Kirsch P. Modern Fluoroorganic Chemistry   Wiley-VCH; Weinheim: 2004. 
  • 21b Chambers RD. Fluorine in Organic Chemistry   Blackwell; Oxford: 2004. 
  • 21c Smart RE. Banks BE. Tatlow JC. Organofluorine Chemistry: Principles and Commercial Applications   Plenum; New York: 1994. 
  • 22a Welch JT. Eswarakrishnan S. Fluorine in Bioorganic Chemistry   Wiley; New York: 1991. 
  • 22b Biomedical Frontiers of Fluorine Chemistry   ACS Symposium Series 639:  Ojima I. McCarthy JR. Welch JT. American Chemical Society; Washington DC: 1996. 
  • 22c Banks RE. Organofluorine Chemicals and their Industrial Applications   Ellis Harwood; New York: 1979. 
  • 22d Peters R. Carbon-Fluorine Compounds Chemistry, Biochemistry and Biological Activities, A Ciba Foundation Symposium   Elsevier; Amsterdam: 1972. 
  • 22e Walsh CT. Annu. Rev. Biochem.  1984,  53:  493 
  • 23 Prakash GKS. Yudin A. Chem. Rev.  1997,  97:  757 
  • 24 Umemoto T. Chem. Rev.  1996,  96:  1757 
  • 25a Petersen PV, Lassen N, Nørgaard J, and Huld T. inventors; US Patent  3467675.  1969; Chem. Abstr. 1967, 66, 37770
  • 25b DeBernardis JF. Arendsen DL. Kyncl JJ. Kerman DJ. J. Med. Chem.  1987,  30:  178 
  • 25c Dem’yanovich VM. Shishkina IN. Kuznetsova AA. Potekhin KA. Chesnova AV. Russ. J. Org. Chem.  2006,  42:  986 
  • 26a Filler R. Kobayashi Y. Yagupolskii LM. Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications   Elsevier; New York: 1993. 
  • 26b Müller K. Faeh C. Diederich F. Science  2007,  317:  1881 
  • 26c Purser S. Moore PR. Swallow S. Gouverneur V. Chem. Soc. Rev.  2008,  37:  320 
  • 26d Hagmann WK.
    J. Med. Chem.  2008,  51:  4359 
  • 27a Mitsunobu O. Synthesis  1981, 
  • 27b Hughes DL. Org. React.  1992,  42:  335 
  • 27c Mitsunobu O. Eguchi M. Bull. Chem. Soc. Jpn.  1971,  44:  3427 
  • 27d Hughes DL. Org. Prep. Proced. Int.  1996,  28:  127 
  • 27e Mcnulty J. Capretta A. Laritchev V. Dyck J. Robertson AJ. Angew. Chem. Int. Ed.  2003,  42:  4051 
  • 28a Dembinski R. Eur. J. Org. Chem.  2004,  2763 
  • 28b Ito S. Tsunoda T. Pure Appl. Chem.  1999,  71:  1053 
  • 28c Dandapani S. Curran DP. Chem. Eur. J.  2004,  10:  3130 
  • 28d But TYS. Toy PT. J. Am. Chem. Soc.  2006,  128:  9636 
  • 29 Tsunoda T. Otsuka J. Yamamiya Y. Ito S. Chem. Lett.  1994,  3:  539 
  • 30 Tsunoda T. Ozaki F. Shirakata N. Tamaoka Y. Yamamoto H. Ito S. Tetrahedron Lett.  1996,  37:  2463 
  • 31 Garcia-Delgado N. Riera A. Verdaguer X. Org. Lett.  2007,  9:  635 
  • 32 Richard JP. Amyes TL. Bei L. Stubblefield V. J. Am. Chem. Soc.  1990,  112:  9513 
  • 33 Smissman EE. Makriyannis A. J. Org. Chem.  1973,  38:  1652 
  • 34 Landge SM. Borkin DA. Török B. Tetrahedron Lett.  2007,  48:  6372 
  • 35 Marshall LJ. Roydhouse MD. Slawin AMZ. Walton JC. J. Org. Chem.  2007,  72:  898 
  • 36 Faust R. Garratt PJ. Jones R. Yeh L.-H. J. Med. Chem.  2000,  43:  1050 
  • 37 Prakash GKS. Krishnamurti R. Olah GA. J. Am. Chem. Soc.  1989,  111:  393 
  • 38 Blagg BSJ. Poulter CD. J. Org. Chem.  1999,  64:  1508 
  • 39 Brewer ARE. Drake AF. Gibson SE. Rendell JT. Tetrahedron  2008,  64:  6615 
  • 40 Zhang F. Peng Y. Liao S. Gong Y. Tetrahedron  2007,  63:  4636 
  • 41 Paleta O. Palecek J. Dolensky B. J. Fluorine Chem.  2001,  111:  175 
  • 42 Prakash GKS. Hu J. Wang Y. Olah GA. Eur. J. Org. Chem.  2005,  2218 
  • 43 Kawashima T. Ohno F. Okazaki R. Ikeda H. Inagaki S. J. Am. Chem. Soc.  1996,  118:  12455