(-)-Quinic acid has been converted into derivatives of a furo[3,2-b]furan-2-one system using Wittig olefination reactions of lactones. Studies for this transformation included the use of microwave-assisted reactions. © Georg Thieme Verlag Stuttgart. 1930453049Barco, A., Benetti, S., De Risi, C., Marchetti, P., Pollini, G.P., Zanirato, V., (1997) Tetrahedron: Asymmetry, 8, p. 3515Garg, N.K., Caspi, D.D., Stoltz, B.M., (2005) J. Am. Chem. Soc, 127, p. 5970Hanessian, S., Wang, J., Montgomery, D., Stoll, V., Stewart, K.D., Kati, W., Maring, C., Laver, W.G., (2002) Bioorg. Med. Chem. Lett, 12, p. 3425Matsuo, K., Matsumoto, T., Nishiwaki, K., (1998) Heterocycles, 48, p. 1213Matsuo, K., Sugimura, W., Shimizu, Y., Nishiwaki, K., Kuwajima, H., (2000) Heterocycles, 53, p. 1505Baptistella, L.H.B., Cerchiaro, G., (2004) Carbohydr. Res, 339, p. 665Barnwell, M.G., Hungerford, N.L., Jolliffe, K.A., (2004) Org. Lett, 6, p. 2737Cytotoxic compounds isolated from plants of Goniothalamus species. See: (a) Ruiz, P.Murga, J.Carda, M.Marco, J. A. J. Org. Chem. 2005, 70, 713Lopez-Lazaro, M., Martin-Cordero, C., Bermejo, A., Cortés, D., Ayuso, M.J., (2001) Anticancer Res, 21, p. 3493Li, R.-T., Li, S.-H., Zhao, Q.-S., Lin, Z.-W., Sun, H.-D., Lu, Y., Wang, C., Zheng, Q.-T., (2003) Tetrahedron Lett, 44, p. 3531. , Found in plants of Schisandraceae family, used in Chinese traditional medicine. SeeIsolated from plants of Scrophularia species and used in Asian herbal medicine. See: Han, J. S.Lowary, T. L. J. Org. Chem. 2003, 68, 4116Isolated from Stemona species, which present insecticidal activities. See: Kaltenegger, E.Brem, B.Mereiter, K.Kalchhauser, H.Kählig, H.Hofer, O.Vajrodaya, S.Greger, H. Phytochemistry 2003, 63, 803A potent enzyme activator used for cardiac irregularities, isolated from Caribbean sponges of the genus Plakortis. See: Hayes, P. Y.Kitching, W. J. Am. Chem. Soc. 2002, 124, 9718Mereyala, H.B., Gadikota, R.R., (2000) Tetrahedron: Asymmetry, 11, p. 743. , Compounds found in braconid wasps. SeeMurphy, P.J., Brennan, J., (1988) Chem. Soc. Rev, 17, p. 1. , and references cited thereinLakhrissi, M., Chapleur, Y., (1996) Angew. Chem., Int. Ed. Engl, 35, p. 750Lakhrissi, Y., Taillefumier, C., Lakhrissi, M., Chapleur, Y., (2000) Tetrahedron: Asymmetry, 11, p. 417Sabitha, G., Reddy, M.M., Srinivas, D., Yadov, J.S., (1999) Tetrahedron Lett, 40, p. 165Microwave labstation MicroSYNTH (Millestone) operating at 2.45 GHz, dual magnetron system with delivered microwave power of 1000 W (pulsed irradiation), equipped with a thermocouple temperature control system. All experiments were conduced in sealed vessels (20 mL - the of the reactions were no more than 10% of this) with magnetic stirringThe lactone 3 was recovered intact when treated, with or without the assistance of microwaves, with diethylphosphonoacetate and bases (Horner-Wadsworth-Emmons olefinations)Batches of several reaction mixtures were combined for chromatographic purificationReaction of Lactone 3 with Ph3PCHCOOEt under Microwave Irradiation A 20 mL microwave vessel (for reactions up to 4 bar) containing a mixture of 3 (200 mg, 0.93 mmol, freshly distilled chlorobenzene (2 mL, and ethoxycarbonyl-methylene(triphenyl) phosphorane (5, 500 mg, 1.43 mmol) was connected to a temperature sensor, and the apparatus was irradiated for 1 h in a microwave equipment programmed for temperature control: 15 min to reach 180°C and then 1 h at this temperature. After cooling, the mixture was evaporated. The residue was purified by silica gel column chromatography (hexane-EtOAc 15, to give 6 (39, and 8 (46, besides unchanged lactone 3 (10, When batches of several reaction mixtures were combined for chromatographic purification, compounds 7 (7, 9 (1, and 10 (4, were also isolated. Compound 6: [α]D 20 47.6 (c 0.58, CHCl3, IR film, νDesmaële, D., (1996) Tetrahedron Lett, 37, p. 1233Bittner, C., Burgo, A., Murphy, P.J., Sung, C.H., Thornhill, A.J., (1999) Tetrahedron Lett, 40, p. 3455Preparation of 8 via the Bromoacetyl Derivative 12 1) A solution of 3 (200 mg, 0.93 mmol) in anhyd Et2O (15 mL, under argon atmosphere, was stirred at 0°C, and anhyd pyridine (100 μL, 1.2 mmol) was added, followed by bromoacetyl bromide (100 μL, 1.15 mmol, The solution was slowly warmed to r.t, in the absence of light, and the stirring was maintained for 2 h. Then, H2O (15 mL) was added and the aqueous layer was separated and extracted two more times with Et2O (15 mL, The combined organic layers were washed sequentially with H2O (25 mL, sat. CuSO4 solution (25 mL, H2O (25 mL) and brine (25 mL, separated, and dried (MgSO4, After filtration, the solvent was concentrated to give crude 12 in 89% yield (278 mg, used without purification in the next step. For characterization, a small sample was purified by flash chromatography hexane-EtOAc 20, to give 12 as white crSmall signals, always presented on the spectral data of crude 19, were attributed to the C7-epimer of 19 (less than 8% yield). This compound probably arises from a minor C7-epimer of the dialdehyde 18. A seven-membered lactone, possible by intramolecular transesterification reaction of 19, was not observed.Data for Compound 21, 4S,5 S,7S)-7-(2-Phenylethyl)-5-(3-phenylpropyl) tetrahydrofuro|3,2-b]furan-2 (3H)-one, α]D20 -14.5 (c 0.27, CHCl3, IR (film, νmax, 1779 cm-1. 1H NMR (500 MHz, CDCl3, δ, 1.59 (dd, 1 H, J, 10.3, 13.4 Hz, 1.70-1.97 (m, 6 H, 2.37 (dd, 1 H, J, 4.6, 13.4 Hz, 2.61-2.79 (m, 4 H, 2.65 (d, 1 H, J, 18.8 Hz, 2.79 (dd, 1 H, J, 6.2, 18.8 Hz, 4.46 (d, 1 H, J, 6.2 Hz, 4.73 (m, 1 H, 7.16-7.34 (m, 10 H, 13C NMR (125 MHz, CDCl3, δ, 26.0, 32.2, 35.6, 36.2, 36.3, 37.0, 42.8, 77.7, 80.7, 96.5, 125.9, 126.0, 128.2, 128.3, 128.4, 141.2, 141.3, 175.5. HRMS EI, m/z calcd for C23H26O3: 350.45094found: 350.45186