Synlett 2013; 24(18): 2383-2388
DOI: 10.1055/s-0033-1339755
letter
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of Fluoroalkylated Butanolides

Holger Erdbrink
Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany   Fax: +49(30)83853625   Email: cczekeli@chemie.fu-berlin.de
,
Constantin Czekelius*
Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany   Fax: +49(30)83853625   Email: cczekeli@chemie.fu-berlin.de
› Author Affiliations
Further Information

Publication History

Received: 31 July 2013

Accepted after revision: 19 August 2013

Publication Date:
05 September 2013 (online)


Abstract

Starting from fluoroalkylated, optically active acyl oxazolidinones the corresponding di- and trisubstituted butanolides were prepared in enantiomerically pure form. Using a divergent synthetic route highly functionalized fluoroalkylated building blocks are accessible.

Supporting Information

 
  • References and Notes


    • For general reviews, see:
    • 2a McClinton MA, McClinton DA. Tetrahedron 1992; 48: 6555
    • 2b Umemoto T. Chem. Rev. 1996; 96: 1757
    • 2c Prakash GK. S, Yudin AK. Chem. Rev. 1997; 97: 757
    • 2d Billard T, Langlois BR. Eur. J. Org. Chem. 2007; 891
    • 2e Ma J.-A, Cahard D. Chem. Rev. 2008; 108: PR1
    • 2f Sato K, Tarui A, Omote M, Ando A, Kumadaki I. Synthesis 2010; 1865
    • 2g Roy S, Gregg BT, Gribble GW, Le V.-D, Roy S. Tetrahedron 2011; 67: 2161
    • 2h Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475
    • 2i Macé Y, Magnier E. Eur. J. Org. Chem. 2012; 2479

      For recent reviews, see:
    • 3a Czekelius C, Tzschucke CC. Synthesis 2010; 543
    • 3b Qiu X.-L, Qing F.-L. Eur. J. Org. Chem. 2011; 3261
    • 3c Mikami K, Fustero S, Sánchez-Roselló M, Aceña JL, Soloshonok V, Sorochinsky A. Synthesis 2011; 3045
    • 3d Nie J, Guo H.-C, Cahard D, Ma J.-A. Chem. Rev. 2011; 111: 455
  • 4 Erdbrink H, Peuser I, Gerling UI. M, Lentz D, Koksch B, Czekelius C. Org. Biomol. Chem. 2012; 10: 8583
    • 5a Reiser O, Seitz M. Curr. Opin. Chem. Biol. 2005; 9: 285
    • 5b Kitson RR. A, Millemaggi A, Taylor RJ. K. Angew. Chem. Int. Ed. 2009; 48: 9426
    • 5c Popsavin V, Benedeković G, Sréco B, Popsavin M, Francuz J, Kojić V, Bogdanović G. Org. Lett. 2007; 9: 4235
    • 5d Larrosa I, Da Silva MI, Gómez PM, Hannen P, Ko E, Lenger SR, Linke SR, White AJ. P, Wilton D, Barett AG. M. J. Am. Chem. Soc. 2006; 128: 14042
    • 5e Li Y, Hale KJ. Org. Lett. 2007; 9: 1267
    • 5f Nicolaou KC, Harrison ST. J. Am. Chem. Soc. 2007; 129: 429

      For selected reviews, see:
    • 6a Hein M, Miethchen R In Advances in Organic Chemistry . Vol. 2. Atta-Ur-Rahman x, Laali KK. Bentham Science Publishers; Oak Park, IL: 2006: 381-429
    • 6b Pankiewicz KW. Carbohydr. Res. 2000; 327: 87
    • 6c Card PJ. J. Carbohydr. Chem. 1985; 4: 451
    • 7a Yamauchi C, Kuriyama M, Shimazawa R, Morimoto T, Kakiuchi K, Shirai R. Tetrahedron 2008; 64: 3133
    • 7b Kapferer T, Brückner R. Eur. J. Org. Chem. 2006; 2119
    • 7c Braukmüller S, Brückner R. Eur. J. Org. Chem. 2006; 2110
    • 7d Ley SV, Dixon DJ, Guy RT, Palomero MA, Polara A, Rodríguez F, Sheppard TD. Org. Biomol. Chem. 2004; 2: 3618
    • 7e Greszler SN, Johnson JS. Angew. Chem. Int. Ed. 2009; 48: 3689
    • 7f Babu SA, Yasuda M, Okabe Y, Shibata I, Baba A. Org. Lett. 2006; 8: 3029
    • 7g Pearson AJ, Mesaros EF. Org. Lett. 2002; 4: 2001
    • 7h Takahata H, Uchida Y, Momose T. J. Org. Chem. 1994; 59: 7201
    • 7i Fernandez A.-M, Plaquevent J.-C, Duhamel L. J. Org. Chem. 1997; 62: 4007
    • 7j Peng Z.-H, Woerpel KA. Org. Lett. 2001; 3: 675
    • 7k Chamberlin AR, Dezube M, Reich SH, Sall DJ. J. Am. Chem. Soc. 1989; 111: 6247
    • 8a For a general review, see: Evans DA, Nelson JV, Taber TR. Topics in Stereochemistry 1982; 13: 1
    • 8b Evans DA, Ennis MD, Mathre DJ. J. Am. Chem. Soc. 1982; 104: 1737
    • 9a Peed J, Davies IR, Peacock LR, Taylor JE, Kociok-Köhn G, Bull SD. J. Org. Chem. 2012; 77: 543
    • 9b Davies IR, Cheeseman M, Green R, Mahon MF, Merritt A, Bull SD. Org. Lett. 2009; 11: 2896
    • 9c Dias LC, Finelli FG, Conegero LS, Krogh R, Andricopulo AD. Eur. J. Org. Chem. 2010; 6748
    • 9d Dias LC, de Castro IB. D, Steil LJ, Augusto T. Tetrahedron Lett. 2006; 47: 213
    • 9e Wang Z.-M, Zhang X.-L, Sharpless BK, Sinha SC, Sinha-Bagchi A, Keinan E. Tetrahedron Lett. 1992; 33: 6407
  • 10 Santaniello E, Ponti F, Manzocchi A. Synthesis 1978; 891

    • For the synthesis of related compounds starting from dihydrofuran-2(3H)-one, see:
    • 11a Shinohara N, Haga J, Yamazaki T, Kitazume T, Nakamura S. J. Org. Chem. 1995; 60: 4363
    • 11b Canney DJ, Lu H.-F, McKeon AC, Yoon K.-W, Xu K, Holland KD, Rothmand SM, Ferrendelli JA, Covey DF. Bioorg. Med. Chem. 1998; 6: 43
  • 12 Attempts to synthesize the corresponding fluoroalkylated γ-valerolactons by hydroboration of 4 (9-BBN or BH3·THF, THF, 0 °C) followed by oxidation and lactonization were unsuccessful and gave a complex product mixture along with unreacted starting material.
    • 13a Rüeger H, Stutz S, Göschke R, Spindler F, Maibaum J. Tetrahedron Lett. 2000; 41: 10085
    • 13b Nishikawa K, Nakahara H, Shirokura Y, Nogata Y, Yoshimura E, Umezawa T, Okino T, Matsuda F. Org. Lett. 2010; 12: 904
    • 13c Nishikawa K, Nakahara H, Shirokura Y, Nogata Y, Yoshimura E, Umezawa T, Okino T, Matsuda F. J. Org. Chem. 2011; 76: 6558
    • 14a Evans DA, Rieger DL, Bilodeau MT, Urpi F. J. Am. Chem. Soc. 1991; 113: 1047
    • 14b Evans DA, Bartroli J, Shih TL. J. Am. Chem. Soc. 1981; 103: 2127
    • 15a Crimmins MT, King BW, Tabet EA, Chaudhary K. J. Org. Chem. 2001; 66: 894
    • 15b Crimmins MT, She J. Synlett 2004; 1371
  • 16 Typical Procedure for the TiCl4-Mediated Aldol Reaction of 9a with Acroleine: (S)-4-Benzyl-3-[(2S,3R)-3-hydroxy-2-(3,3,3-trifluoropropyl)pent-4-enoyl]oxazolidin-2-one (10a)The substrate 9a (500 mg, 1.66 mmol, 1.00 equiv) was dissolved in CH2Cl2 (11.3 mL) and TiCl4 (191 μL, 1.74 mmol, 1.05 equiv) was added dropwise to the vigorously stirred solution at 0 °C. The yellow suspension was stirred at 0 °C for 5 min before (–)-sparteine (953 μL, 4.15 mmol, 2.50 equiv) was slowly added. The black solution was stirred at 0 °C for 20 min. Freshly distilled acroleine (144 μL, 2.16 mmol, 1.30 equiv) was added dropwise. The resulting solution was stirred for 3 h at 0 °C. The reaction was then allowed to warm to r.t. and aq half-saturated NH4Cl (10 mL) was added. The aqueous layer was extracted with CH2Cl2 (4 × 10 mL). The combined organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo. The crude product (dr > 95:5, 19F NMR) was purified flash column chromatography (SiO2, EtOAc–hexane = 1:2) to afford 447 mg (75%, 1.25 mmol) of syn-aldol derivate 10a as a light yellow oil; [α]D 22 +42.6 (c 1.00, CHCl3). 1H NMR (500 MHz, CDCl3): δ = 2.27 (br d, J = 2.8 Hz, 1 H, OH), 2.43 (mc, 1 H, CH2CF3), 2.68 (dd, J = 13.4, 10.1 Hz, 1 H, CH 2Ph), 2.83–2.90 (m, 1 H, CH2CF3), 3.35 (dd, J = 13.4, 3.4 Hz, 1 H, CH 2Ph), 4.19–4.20 (m, 2 H, OCH2), 4.44 (mc, 1 H, CHCH=CH2), 4.53 (ddd, J = 10.9, 4.6, 2.0 Hz, 1 H, COCH), 4.69–4.74 (m, 1 H, NCH), 5.29–5.40 (m, 2 H, CHCH=CH 2), 5.88 (ddd, J = 17.0, 10.5, 5.7 Hz, 1 H, CHCH=CH2), 7.21–7.36 (5 H, Ph) ppm. 13C NMR (126 MHz, CDCl3): δ = 31.3 (q, J CF = 29.3 Hz, CH2CF3), 37.4 (CH2Ph), 42.0 (mc, COCH), 55.6 (NCH), 66.2 (OCH2), 72.8 (CHCH=CH2), 117.9 (CHCH=CH2), 126.8 (q, J CF = 277 Hz, CH2 CF3), 127.4 (para ArC), 129.0 (ortho ArC), 129.3 (meta ArC), 135.1 (ArC), 136.2 (CHCH=CH2), 153.4 (OCON), 172.5 (NCOC) ppm. 19F NMR (376 MHz, CDCl3): δ = –64.8 (t, J = 11.0 Hz, 3 F, CF3) ppm. IR (film): 650, 702, 935, 1015, 1102, 1150, 1211, 1260, 1364, 1392, 1700, 1780, 2923, 3483 cm–1. ESI-HRMS: m/z [M + Na]+ calcd. for [C17H18F3NNaO4]+: 380.1080; found: 380.1080.
  • 17 Typical Procedure for the Synthesis of Hydroxy-γ-butyrolactones: (3S,4S,5R)-4-Hydroxy-5-(hydroxymethyl)-3-(2,2,2-trifluoroethyl)dihydrofuran-2(3H)-one (11a)To a stirred suspension of K2OsO4·2H2O (17.3 mg, 0.047 mmol, 10 mol%) in acetone–H2O (8:1, 0.40 mL), NMO (110 mg, 0.940 mmol, 2.00 equiv) was added in one portion at r.t. After 5 min, the mixture was cooled to 0 °C, and a solution of 10a (168 mg, 0.470 mmol, 1.00 equiv) in acetone–H2O (8:1, 1.60 mL) was slowly added. The reaction mixture was stirred at 0 °C and allowed to warm to r.t. overnight (15 h). The reaction was quenched by the addition of 45% aq NaHSO3 solution (0.4 mL) and stirring was continued for 30 min at r.t. After removal of the solvent, the residue was extracted with EtOAc (4 × 2 mL). The combined organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product (dr = 92:8, 19F NMR) was purified by flash column chromatography (SiO2, CH2Cl2–MeOH, 20:1 → 12:1) to afford 52.0 mg (0.242 mmol, 51%) of hydroxy-γ-butyrolactone 11a as colorless solid; mp 92–95 °C; [α]D 22 +21.1 (c 0.50, C3H6O). 1H NMR (500 MHz, C3D6O): δ = 2.55–2.64 (m, 1 H, CH2CF3), 2.67–2.77 (m, 1 H, CH2CF3), 2.94 (mc, 1 H, COCH), 3.73 (ddd, J = 12.6, 6.2, 3.9 Hz, 1 H, CHCH 2OH), 3.91 (ddd, J = 12.6, 5.1, 2.3 Hz, 1 H, CHCH 2OH), 4.26–4.29 (m, 2 H, CHCH2OH, CHCH2OH), 4.37–4.41 (m, 1 H, CHCHOH), 5.02 (d, J = 6.0 Hz, 1 H, CHCHOH) ppm. 13C NMR (126 MHz, C3D6O): δ = 33.4 (q, J CF = 29.9 Hz, CH2 CF3), 44.5 (q, J CF = 2.5 Hz, COCH), 61.1 (CHCH2OH), 72.8 (CHCHOH), 86.3 (CHCH2OH), 128.0 (q, J CF = 276 Hz, CF3), 174.9 (OCOC) ppm. 19F NMR (376 MHz, C3D6O): δ = –64.8 (d, J = 11.3 Hz, CF3) ppm. IR (film): 652, 703, 833, 993, 1047, 1087, 1100, 1162, 1262, 1281, 1444, 1754, 3339, 3491 cm–1. ESI-HRMS: m/z [M + Na]+ calcd for [C7H9F3NaO4]+: 237.0345; found: 237.0349.

    • For other examples of dihydroxylations of allylic alcohols, see ref. 9c and:
    • 18a Donohoe TJ, Waring MJ, Newcombe NJ. Synlett 2000; 149
    • 18b Donohoe TJ, Newcombe NJ, Waring MJ. Tetrahedron Lett. 1999; 40: 6881