Synthesis 2013; 45(15): 2179-2187
DOI: 10.1055/s-0033-1338892
paper
© Georg Thieme Verlag Stuttgart · New York

Alkylation and Ring Opening of Perfluoroalkyl- and Perfluoroaryl-Substituted 2-Siloxycyclopropanecarboxylates Yielding Fluorinated γ-Oxo Esters or β,γ-Unsaturated Ketones

Daniel Gladow
Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany   Fax: +49(30)83855367   Email: hans.reissig@chemie.fu-berlin.de
,
Hans-Ulrich Reissig*
Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany   Fax: +49(30)83855367   Email: hans.reissig@chemie.fu-berlin.de
› Author Affiliations
Further Information

Publication History

Received: 10 April 2013

Accepted after revision: 30 April 2013

Publication Date:
17 June 2013 (online)


Abstract

Deprotonation of perfluoroalkyl- and perfluorophenyl-substituted methyl 2-siloxycyclopropanecarboxylates and subsequent reaction with alkyl halides furnished C-1 alkylated cyclopropanes with high diastereoselectivities. Smooth triethylamine trishydrofluoride mediated desilylation and ring opening afforded the corresponding γ-oxo esters in good to excellent yields. Treatment of methyl 2-siloxycyclopropanecarboxylates with Grignard reagents and subsequent ring opening in the presence of acid provided β,γ-unsaturated ketones with fluorine-containing substituents.

Supporting Information

 
  • References


    • For reviews on donor–acceptor cyclopropanes, see:
    • 1a Reissig H.-U. Top. Curr. Chem. 1988; 144: 73
    • 1b Reissig H.-U, Zimmer R. Chem. Rev. 2003; 103: 1151
    • 1c Gnad F, Reiser O. Chem. Rev. 2003; 103: 1603
    • 1d Yu M, Pagenkopf BL. Tetrahedron 2005; 61: 321
    • 1e De Simone F, Waser J. Synthesis 2009; 3353
    • 1f Carson CA, Kerr MA. Chem. Soc. Rev. 2009; 38: 3051

    • For an interesting theoretical study on donor–acceptor cyclopropanes, see:
    • 1g Schneider TF, Werz DB. Org. Lett. 2011; 13: 1848

    • For a recent example of fluorinated cyclopropanes, see:
    • 1h Ivashkin P, Couve-Bonnaire S, Jubault P, Pannecoucke X. Org. Lett. 2012; 14: 2270

      Selected reviews:
    • 2a Shimizu M, Hiyama T. Angew. Chem. 2005; 117: 218 ; Angew. Chem. Int. Ed. 2005, 44, 214
    • 2b Ma J.-A, Cahard D. J. Fluorine Chem. 2007; 128: 975

    • For recent original reports, see:
    • 2c Prakash GK. S, Jog PV, Batamack PT. D, Olah GA. Science 2012; 338: 1324
    • 2d Fujiwara Y, Dixon JA, O’Hara F, Funder ED, Dixon DD, Rodriguez RA, Baxter RD, Herle B, Sach N, Collins MR, Ishihara Y, Baran PS. Nature 2012; 492: 95
  • 4 Gladow D, Reissig H.-U. Helv. Chim. Acta 2012; 95: 1818
  • 5 Laub HA, Gladow D, Reissig H.-U, Mayr H. Org. Lett. 2012; 14: 3990

    • For selected publications dealing with in situ generation of carbonyl compounds from d–a cyclopropanes and their direct subsequent functionalization in one-pot procedures, see:
    • 6a Reichelt I, Reissig H.-U. Synthesis 1984; 786
    • 6b Grimm EL, Reissig H.-U. J. Org. Chem. 1985; 50: 242
    • 6c Ullmann A, Schnaubelt J, Reissig H.-U. Synthesis 1998; 1052
    • 6d Zimmer R, Ziemer A, Gruner M, Brüdgam I, Hartl H, Reissig H.-U. Synthesis 2001; 1649
    • 6e Veljkovic I, Zimmer R, Reissig H.-U, Brüdgam I, Hartl H. Synthesis 2006; 2677
    • 6f Özbek H, Veljkovic IS, Reissig H.-U. Synlett 2008; 3145
    • 6g Beyzavi MH, Lentz D, Reissig H.-U, Wiehe A. Eur. J. Org. Chem. 2013; 269
    • 7a Reissig H.-U, Böhm I. J. Am. Chem. Soc. 1982; 104: 1735
    • 7b Reichelt I, Reissig H.-U. Chem. Ber. 1983; 116: 3895
    • 7c Kunkel E, Reichelt I, Reissig H.-U. Liebigs Ann. Chem. 1984; 512
    • 8a Reissig H.-U, Hirsch E. Angew. Chem. 1980; 92: 839 ; Angew. Chem., Int. Ed. Engl. 1980, 19, 813
    • 8b Kunkel E, Reichelt I, Reissig H.-U. Liebigs Ann. Chem. 1984; 802
  • 9 Review on the use of triethylamine trishydrofluoride in organic synthesis: McClinton MA. Aldrichimica Acta 1995; 28: 31
    • 10a Zschiesche R, Grimm EL, Reissig H.-U. Angew. Chem. 1986; 98: 1104 ; Angew. Chem., Int. Ed. Engl. 1986, 25, 1086
    • 10b Reissig H.-U, Reichelt I, Kunz T. Org. Synth. 1992; 71: 189
    • 11a Gelb MH, Svaren JP, Abeles RH. Biochemistry 1985; 24: 1813
    • 11b Bégué J.-P, Bonnet-Delpon D. Tetrahedron 1991; 47: 3207
    • 11c Linderman RJ, Jamois EA. J. Fluorine Chem. 1991; 53: 79
    • 11d McClinton MA, McClinton DA. Tetrahedron 1992; 48: 6555
    • 11e Kiselyov AS, Strekowski L. Org. Prep. Proced. Int. 1996; 28: 289
    • 11f Singh RP, Shreeve JM. J. Org. Chem. 2000; 65: 3241
    • 11g Kokotos G, Hsu Y.-H, Burke JE, Baskakis C, Kokotos CG, Magrioti V, Dennis EA. J. Med. Chem. 2010; 53: 3602
    • 11h Ilies M, Dowling DP, Lombardi PM, Christianson DW. Bioorg. Med. Chem. Lett. 2011; 21: 5854
    • 11i Zhao Q.-Y, Huang L, Wei Y, Shi M. Adv. Synth. Catal. 2012; 354: 1926
    • 11j Zheng Y, Xiong H.-Y, Nie J, Hua M.-Q, Ma J.-A. Chem. Commun. 2012; 48: 4308
    • 11k Sun L, Wang T, Ye S. Chin. J. Chem. 2012; 30: 190
    • 11l Zhang P, Wolf C. J. Org. Chem. 2012; 77: 8840
    • 11m Rudzinski DM, Kelly CB, Leadbeater NE. Chem. Commun. 2012; 48: 9610
    • 11n Yang D, Zhou Y, Xue N, Qu J. J. Org. Chem. 2013; 78: 4171
  • 12 Wan W, Hou J, Jiang H, Wang Y, Zhu S, Deng H, Hao J. Tetrahedron 2009; 65: 4212
    • 13a Tamborski C, Soloski EJ. J. Org. Chem. 1966; 31: 746

    • For a mechanistic study, see:
    • 13b Kvíčala J, Beneš M, Paleta O, Král V. J. Fluorine Chem. 2010; 131: 1327

    • For substitution by organolithium species, see:
    • 13c Coe PL, Oldfield D, Tatlow JC. J. Fluorine Chem. 1985; 29: 341
  • 14 Olah GA, Shih JG, Prakash GK. S. J. Fluorine Chem. 1986; 33: 377
    • 15a Uneyama K, Morimoto O, Nanbu H. Tetrahedron Lett. 1989; 30: 109
    • 15b King JF, Gill MS. J. Org. Chem. 1996; 61: 7250
    • 16a Suda M, Fukushima A. Chem. Lett. 1981; 103
    • 16b Suda M. Tetrahedron Lett. 1981; 22: 1421
    • 17a Bretsch W, Reissig H.-U. Liebigs Ann. Chem. 1987; 175

    • For similar reactions of other cyclopropanes see:
    • 17b Julia M, Le Thuillier G. Bull. Soc. Chim. Fr. 1966; 717
    • 17c Julia M, Le Thuillier G. Bull. Soc. Chim. Fr. 1966; 729
    • 18a Paal C. Ber. Dtsch. Chem. Ges. 1884; 17: 2756
    • 18b Paal C. Ber. Dtsch. Chem. Ges. 1884; 17: 2863
    • 18c Paal C. Ber. Dtsch. Chem. Ges. 1885; 18: 367
  • 19 Shi G, Xu Y. J. Org. Chem. 1990; 55: 3383