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Synlett 2014; 25(6): 817-820
DOI: 10.1055/s-0033-1340739
DOI: 10.1055/s-0033-1340739
letter
Prins Cyclization Using Magnesium Halides: Mild Access to 4-Halogenated Polysubstituted Tetrahydropyrans with a Special Feature
Further Information
Publication History
Received: 20 December 2013
Accepted after revision: 13 January 2014
Publication Date:
13 February 2014 (online)
Abstract
Different 4-halo-substituted polyfunctionalized tetrahydropyrans were easily synthesized by segment-coupling Prins cyclization utilizing magnesium halides. The moderate Lewis acidity allows transformation of substrates bearing acid-labile functional groups. A solvent dependency of the stereochemistry at the C4 carbon was observed.
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References and Notes
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- 16 General Procedure for Prins Cyclization of 8 Magnesium halide (2 equiv) was added to a solution of acetoxy ether 8 in the respective solvent (mixture; 5–10 mL/mmol of 8) at given temperatures. Reaction mixture was stirred for 1–2 h and quenched with sat. NaHCO3 solution and extracted three times with CH2Cl2. The combined organic extracts were washed with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography (pentane–Et2O, 7:1). Spectroscopical Data for (2R,3S,4R,6R)-2-(2-Benzyloxyethyl)-4-bromo-6-[(4R,5S)-2,2-dimethyl-5-vinyl-1,3-dioxolan-4-yl]-3-methyltetrahydropyran (7a) Yield 82%; colorless oil; [a]D +43 (c 2.00, CHCl3). 1H NMR (600 MHz, CDCl3): δ = 7.27–7.37 (5 H, m, C6H5), 5.83 (1 H, ddd, J = 16.8, 10.0, 6.5 Hz, CH=CH2), 5.34 (1 H, dd, J = 17.1, 1.5 Hz, CH=CH 2), 5.14 (1 H, d, J = 10.5 Hz, CH=CH 2), 4.64 (1 H, dd, J = 6.3, 6.3 Hz, CHCH=CH2), 4.44–4.51 (2 H, m, CH2Ph), 4.42 (1 H, dt, J = 12.8, 4.3 Hz, H-4), 3.97 (1 H, dd, J = 8.4, 6.3 Hz, 6-CH), 3.39–3.52 (1 H, m, H-2), 3.48–3.52 (2 H, m, CH2CH 2OBn), 3.36 (1 H, td, J = 9.8, 2.4 Hz, H-6), 2.20 (1 H, dt, J = 10.2, 2.8 Hz, H-5), 1.92–1.99 (2 H, m, H-5 and H-3), 1.78–1.85 (1 H, m, CH 2CH2OBn), 1.60–1.66 (1 H, m, CH 2CH2OBn), 1.45 [3 H, s, C(CH3)2], 1.36 [3 H, s, C(CH3)2], 1.07 (3 H, d, J = 6.9 Hz, 3-CH3). 13C NMR (100 MHz, CDCl3): δ = 138.2 (Car,q), 133.6 (CH=CH2), 128.4 (Car), 127.6 (Car), 117.4 (CH=CH2), 108.7 [C(CH3)2], 79.2 (6-CH), 78.6 (CHCH=CH2), 76.6 (C-2), 76.3 (C6), 73.0 (CH2Ph), 66.9 (CH2 CH2OBn), 54.0 (C-4), 39.7 (C-3), 34.6 (C-5), 33.9 (CH2CH2OBn), 27.7 [C(CH3)2], 25.3 [C(CH3)2], 7.6 (3-CH3). MS: m/z (%) = 424 (70), 422 (70), 301 (50), 231 (75), 141 (55), 137 (70), 127 (100). HRMS: m/z calcd for C22H31BrO4: 438.1403 [M]+; found: 438.1404.
The chiral diol ligand prepared according to: