Synlett, Inhaltsverzeichnis Synlett 2012; 23(12): 1789-1792DOI: 10.1055/s-0031-1290429 letter © Georg Thieme Verlag Stuttgart · New YorkA Total Synthesis of Yellowish Aphid Pigment Furanaphin through Fries Rearrangement Assisted by Boron Trifluoride-Acetic Acid Complex Autor*innen Institutsangaben Taichi Nishimura Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Takeki Iwata Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Hironori Maegawa Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Takeshi Nishii Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Masami Matsugasako Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Hiroto Kaku Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Mitsuyo Horikawa Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Makoto Inai Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Tetsuto Tsunoda* Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Tokushima 770-8514, Japan, Fax: +81(88)6553051 eMail: tsunoda@ph.bunri-u.ac.jp Artikel empfehlen Abstract Artikel einzeln kaufen(opens in new window) Alle Artikel dieser Rubrik(opens in new window) Abstract The yellowish aphid pigment furanaphin, isolated from Aphis spiraecola and possessing cytotoxicity against HL-60 (human promyelocytic leukemia-60) cells, was synthesized by utilizing the Fries rearrangement assisted with a BF3·2AcOH complex as a key step. It was confirmed that the complex effectively mediated the reaction even though the compounds had an electron-withdrawing substituent. Key words Key wordsdyes - pigments - Fries rearrangement - total synthesis - natural products Volltext Referenzen References and Notes 1 Duewell H, Human JP. E, Johnson AW, MacDonald SF, Todd AR. Nature 1948; 162: 759 2 Brown BR, Ekstrand T, Johnson AW, MacDonald SF, Todd AR. J. Chem. Soc. 1952; 4925 3 Cameron DW, Cromartie RI. T, Kingston DG. I, Todd L. J. Chem. Soc. 1964; 51 4 Cameron DW, Chan HW.-S, Kingston DG. I. J. Chem. Soc. 1965; 4363 5 Cameron DW, Chan HW.-S. J. Chem. Soc. C 1966; 1825 6 Bowie JH, Cameron DW, Findlay JA, Quartey JA. K. Nature 1966; 210: 395 7 Banks HJ, Cameron DW. Aust. J. Chem. 1972; 25: 2199 8 Horikawa M, Hashimoto T, Asakawa Y, Takaoka S, Tanaka M, Kaku H, Nishii T, Yamaguchi K, Masu H, Kawase M, Suzuki S, Sato M, Tsunoda T. Tetrahedron 2006; 62: 9072 9 Horikawa M, Tanaka M, Kaku H, Nishii T, Tsunoda T. Tetrahedron 2008; 64: 5515 10 Horikawa M, Hoshiyama T, Matsuzawa M, Shugyo T, Tanaka M, Suzuki S, Sato M, Ito T, Asakawa Y, Kaku H, Nishii T, Inai M, Takahashi S, Tsunoda T. J. Nat. Prod. 2011; 74: 1812 11 Horikawa M, Noguchi T, Takaoka S, Kawase M, Sato M, Tsunoda T. Tetrahedron 2004; 60: 1229 12 Horikawa M, Kikuchi D, Imai T, Tanaka M, Kaku H, Nishii T, Inai M, Takahashi S, Tsunoda T. Heterocycles 2012; 85: 95 13 Losey JE, Ives AR, Harmon J, Ballantyne F, Brown C. Nature 1997; 388: 269 14 Tsuchida T, Koga R, Horikawa M, Tsunoda T, Maoka T, Matsumoto S, Simon J, Fukatsu T. Science 2010; 330: 1102 15 Moran NA, Jarvik T. Science 2010; 328: 624 16a Rizzacasa MA, Sargent MV. Aust. J. Chem. 1987; 40: 1737 16b For an alternative synthetic route to 4, see: Hauser FM, Sengupta D, Corlett SA. J. Org. Chem. 1994; 59: 1967 17a Rizzacasa MA, Sargent MV. Aust. J. Chem. 1988; 41: 1087 17b Singh SB, Graham PL, Reamer RA, Cordingley MG. Bioorg. Med. Chem. Lett. 2001; 11: 3143 18 Blatt AH. Org. React. 1942; 1: 342 19 The Fries rearrangement using the BF3·2CH3CO2H complex was reported. The complex acts as an acyl donor, but the rearrangement of reactants having electron-withdrawing groups was not investigated, see: Davies JS. H, McCrea PA, Norris WL, Ramage GR. J. Chem. Soc. 1950; 3206 20 Fries Rearrangement of 4: To a solution of acetate 4 (104.1 mg, 0.327 mmol) in CH2Cl2 (0.5 mL) was added BF3·2AcOH (440 μL, 3.16 mmol) under an Ar atmosphere, and the resulting mixture was heated at reflux for 30 min. After addition of H2O (3 mL) at 0 °C, the resulting mixture was extracted with CH2Cl2 (3 × 5 mL), and the combined organic extracts were washed with brine (10 mL), dried over MgSO4, filtered, and concentrated. The residue was purified by silica gel column chromatography (n-hexane–EtOAc, 8:1) to give ethyl 3-acetyl-4-hydroxy-5,7-dimethoxy-2-naphthoate (3) in 91% yield as colorless crystals; mp 100–101 °C (EtOAc). 1H NMR (400 MHz, CDCl3): δ = 9.64 (s, 1 H), 7.75 (d, J = 0.4 Hz, 1 H), 6.77 (d, J = 2.0 Hz, 1 H), 6.57 (d, J = 2.0 Hz, 1 H), 4.35 (q, J = 7.2 Hz, 2 H), 4.04 (s, 3 H), 3.90 (s, 3 H), 2.65 (s, 3 H), 1.38 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 203.7, 166.7, 159.0, 157.7, 152.2, 136.5, 128.4, 122.0, 120.7, 111.9, 100.5, 100.2, 61.5, 56.4, 55.5, 31.8, 14.0. IR (ATR): 3329, 1708, 1624, 1578, 1364, 1250, 1198, 1153, 1111, 1045 cm–1. MS (EI): m/z (%)= 318 [M]+, 303, 275 (100). HRMS (EI): m/z calcd for C17H18O6: 318.1103; found: 318.1128 21 Furanaphin (1): Orange-yellow needles (MeOH); mp 218–219 °C (MeOH) {Lit11 211–214 °C (dec)}. 1H NMR (400 MHz, acetone-d 6): δ = 14.28 (s, 1 H), 9.17 (s, 1 H), 6.40 (dd, J = 2.4, 2.4 Hz, 1 H), 6.35 (d, J = 2.4 Hz, 1 H), 6.17 (d, J = 2.4 Hz, 1 H), 5.51 (d, J = 2.4 Hz, 2 H), 2.67 (s, 3 H). 13C NMR (100 MHz, acetone-d 6): δ = 184.8, 184.3, 167.4, 164.7, 143.9, 143.5, 115.2, 111.7, 107.4, 104.7, 100.5, 77.6, 16.1. IR (ATR): 3333, 1650, 1569, 1382, 1170, 1153, 1130, 1085, 985, 887, 823 cm–1. MS (EI): m/z (%) = 231 [M+H]+, 230 (100) [M]+. HRMS (EI): m/z calcd for C13H10O4: 230.0579; found: 230.0575
