аЯрЁБс>ўџ @Bўџџџ?џџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџџьЅС9 №П.5bjbj§Я§Я .JŸЅŸЅ—џџџџџџlиииииииьИИИИ<єьѓ R T T T T T T $§ иx 5иx *ии­ ***ииR *R *ќ*& ии&  њИљ СьЬИ& & ,У 0ѓ & ѕѕ& *ььиииий Supplementary materail for the communication entitled: Unexpected reactivity of acetylenic w№-ketoesters towards TBAF and t-BuOK ; new cascade reactions affording allene and oxetane derivatives. Florence Wendling, Michel Miesch* Universitщ Louis Pasteur, Institut de Chimie  LCOS, 1, rue Blaise Pascal BP296/R8 67008 Strasbourg cedex France. General Procedure for the synthesis of allene derivatives : To a stirred solution of acetylenic w№-ketoesters 6, 7, 8, 17 or 18 (1 eq.; 0.4 mmol) in dry THF (5 mL) was added at room temperature a 1M solution of TBAF in THF (1 eq.; 0.4 mmol). The yellow solution was stirred at room temperature for 30 minutes, hydrolyzed with water (10 mL) and extracted with Et2O (2x10 mL). The organic layers were then washed with a saturated NaCl solution (10 mL), dried over MgSO4, filtered and concentrated under reduced pressure (15 Torr, 25АC). The residue was chromatographed on a silica gel column (15g SiO2; ethyl acetate / hexane 10/90 then 20/80) to afford the corresponding allene derivatives 16, 19, 20, 21 or 22. Allene 16 [ (+) polar] : colorless oil. 1H NMR (CDCl3, 400 MHz) : d№ 1.28 (t, J = 7.2 Hz, 3H); 1.38-1.45 (m, 1H); 1.61-2.09 (m, 10H), 2.13-2.21 (m, 1H); 4.18 (q, J = 7.2 Hz, 2H), 5.64 (dd, J = 3.0, 1.4 Hz, 1H). 13C-NMR (CDCl3, 100 MHz) : d№ №14.2, 20.0, 23.8, 27.6, 27.8, 28.1, 37.2, 47.5, 60.7, 79.4, 89.4, 111.7, 166.5, 207.6. IR (CCl4) : 3550, 3350, 1960, 1719 cm-1. Allene 16 [ (-) polar] : colorless oil. 1H NMR (CDCl3, 400 MHz) : d№ 1.27 (t, J = 7.2 Hz, 3H); 1.48-1.85 (m, 1H); 1.88-2.02 (m, 10H), 2.06-2.13 (m, 1H); 2.21-2.28 (m, 1H); 2.39-2.45 (m, 1H); 4.15-4.29 (m, 2H), 5.66 (t, J = 2.0 Hz, 1H). 13C-NMR (CDCl3, 100 MHz) : d№ №14.2, 20.1, 23.9, 27.7, 27.9, 28.1, 37.3, 47.7, 60.7, 79.5, 89.6, 111.7, 166.4, 207.5. IR (CCl4) : 3550, 3350, 1960, 1716 cm-1. Allene 19 [mixture of the two isomers; isomer A (isomer B)] : colorless oil. 1H NMR (CDCl3, 200 MHz) : d№ 1.00 (0.98) (s, 3H); 1.27 (1.25) (t, 3H, J = 7.1 Hz); 1.29-2.00(m, 10H); 2.19-2.44 (m, 3H); 4.09-4.26 (m, 2H); 5.62-5.67 (m, 1H). 13C-NMR (CDCl3, 50 MHz) : d№ №14.2, 18.9 (18.7), 20.1 (19.8), 22.8 (22.6), 28.4 (28.9), 35.7 (34.9), 36.7 (35.9), 37.7 (36.1), 48.0 (46.8), 60.7 , 81.8 (80.9), 90.0 (89.7), 113.0 (112.0), 166.8, 208.0 (207.0). IR (CCl4) : 1950, 1717 cm-1. Allene 20 [ (+) polar] : colorless oil. 1H NMR (CDCl3, 200 MHz) : d№ 1.07 (s, 3H); 1.24 (t, 3H, J = 7.1 Hz), 1.27-3.27 (m, 15H), 4.03-4.22 (m, 2H), 5.58-5.61(m, 1H). 13C-NMR (CDCl3, 50 MHz) : d№ №14.3, 21.1, 21.4, 22.4, 26.3, 28.3, 31.8, 33.2, 33.2, 33.9, 63.7, 74.4, 88.4, 111.9, 167.0, 207.2. IR (CCl4) : 3594, 3408, 1959, 1716 cm-1. Allene 21 [ (+) polar] : white crystals. M.p. 116-118АC. 1H NMR (CDCl3, 400 MHz) : d№ 1.27 (t, J = 7.2 Hz, 3H); 1.27-2.68 (m, 16H); 4.16 (m, 2H); 5.61 (d, J = 3.5, 1H). 13C-NMR (CDCl3, 100 MHz) : d№ №14.3, 21.6, 26.2, 26.4, 27.0, 28.0, 28.5, 37.1, 45.5, 60.8, 70.5, 88.6, 114.0, 167.0, 207.0. IR (CCl4) : 3500, 3350, 1959, 1717 cm-1 Allene 21 [ (-) polar] : colorless oil. 1H NMR (CDCl3, 400 MHz) : d№ 1.25 (t, 3H, J = 7.2 Hz), 1.24-2.55 (m, 16H), 4.05-435 (m, 2H), 5.53 (d, 1H, J = 3.8 Hz). 13C-NMR (CDCl3, 100 MHz) : d№ 14.3, 21.5, 25.9, 26.5, 27.1, 28.1, 28.5, 36.8, 45.7, 60.5, 70.6, 88.6, 113.4, 166.3, 207.2. IR (CCl4) : 3500, 3350, 1959, 1717 cm-1. Allene 22 [ (+) polar] : colorless oil. 1H NMR (CDCl3, 200 MHz) : d№ 1.23 (t, 3H, J = 7.2 Hz), 1.25-1.27 (m, 15H), 2.36-2.62 (m, 3H), 4.04-4.30 (m, 2H), 5.54-5.58 (m, 1H). 13C-NMR (CDCl3, 50 MHz) : d№ №14.3, 21.0, 22.8, 26.4, 27.1, 27.6, 29.5, 30.0, 40.7, 49.0, 60.7, 75.0, 88.8, 113.2, 166.2, 208.1. IR (CCl4) : 3520, 2934, 1960, 1717 cm-1. Allene 22 [ (-) polar] : colorless oil. 1H NMR (CDCl3, 200 MHz) d№ 1.26 (t, 3H, J = 7.2 Hz), 1.23-1.95 (m, 15H), 2.20-2.50 (m, 3H), 4.06-4.24 (m, 2H), 5.51 (d, 1H, J = 3.7 Hz). 13C-NMR (CDCl3, 50 MHz) : d№ №14.3, 20.9, 26.6, 27.2, 27.4, 28.3, 29.8, 30.0, 41.0, 49.0, 60.5, 73.7, 88.4, 114.3, 166.4, 207.2. IR (CCl4) : 3530, 2940, 1960, 1717 cm-1. General Procedure for the synthesis of oxetane derivatives : To a stirred solution of acetylenic w№-ketoesters 7, 8, 17 or 18 (1 eq.; 0.4 mmol) in dry THF (3 mL) was added at room temperature potassium tert-butoxide (1 eq.; 0.4 mmol). The solution was stirred at room temperature for 30 minutes, hydrolyzed with water (10 mL) and extracted with Et2O (2x10 mL). The organic layers were then washed with a saturated NaCl solution (10 mL), dried over MgSO4, filtered and concentrated under reduced pressure (15 Torr, 25АC). The residue was chromatographed on a silica gel column (15g SiO2; hexane, ethyl acetate / hexane 2/98) to afford the corresponding oxetane derivatives, 24, 25, 26 or 27. Oxetane 24 [ (+) polar] : colorless oil. 1H NMR (CDCl3, 500 MHz) :d№ № 1.03 (s, 3H), 1.24 (t, 3H, J = 7.1 Hz), 1.40-1.70 (m, 8H), 1.76 (tt, 1H, J = 14.2, 4.5 Hz), 1.95 (dt, 1H, J = 12.5, 6.1 Hz), 2.15-2.20 (m, 2H), 3.54 (ddd, 1H, J = 8.9, 3.5, 1.9 Hz), 4.09, 4.12 (ABX3, 2H, JAB = 14.4 Hz, J = 7.1Hz), 5.09 (d, 1H, J = 1.9 Hz). 13C-NMR (CDCl3, 125 MHz) d№ 14.5, 18.7, 20.7, 24.3, 25.5, 37.4, 40.2, 41.9, 42.0, 47.4, 59.3, 89.6, 98.1, 167.8, 181.7. IR (CCl4) : 1709, 1660, 1462 cm-1 Oxetane 25 [ (+) polar] : colorless oil. 1H NMR (CDCl3, 500 MHz) : d№ 0.95 (s, 3H); 1.11-1.20 (m, 2H); 1.25 (t, J = 7.1 Hz, 3H); 1.33-1.79 (m, 11H); 2.02 (td, J = 12.8, 4.3 Hz, 1H); 3.05 (td, J = 5.7, 1.6 Hz, 1H); d№A = 4.08, d№B = 4.15 (ABX3, 2H JAB = 16.5 Hz; J = 7.1 Hz); 4.72 (d, J = 1.5 Hz, 1H). 13C-NMR (CDCl3, 125 MHz) : d№ №14.5, 15.0, 20.0, 20.8, 21.0, 23.5, 30.5, 34.1, 35.6, 36.3, 45.5, 59.1, 87.3, 93.6, 165.7, 178.5. IR (CCl4) : 1714, 1670, 1447 cm-1. Oxetane 25 [ (-) polar] : colorless oil. 1H NMR (CDCl3, 500 MHz) : d№ 1.00 (s, 3H); 1.18-1.28 (m, 2H); 1.23 (t, J = 7.1 Hz, 3H); 1.38-1.93 (m, 10H), 1.99 (td, J = 12.3, 3.7 Hz, 1H); 2.32-2.39 (m, 1H); 3.40 (td, J = 6.2, 1.9 Hz, 1H); d№A = 4.11, d№ B = 4.13 (ABX3, JAB = 10.2 Hz; J = 7.1 Hz); 5.18 (d, J = 1.9 Hz, 1H). 13C-NMR (CDCl3, 125 MHz) : d№ 14.5, 16.0, 19.3, 21.0, 21.1, 23.7, 31.3, 34.0, 36.1, 36.3, 46.9, 59.2, 90.8, 93.7, 167.8, 181.5. IR (CCl4) : 1709, 1657, 1470 cm-1. Oxetane 26 (only one isomer observed): colorless oil. 1H NMR (CDCl3, 200 MHz) : d№ 1.26 (t, 3H, J = 7.1 Hz); 1.28-2.20 (m, 15H), 3.34 (td, 1H, J = 6.0, 1.5 Hz), 4.12 (m, 2H), 5.18 (d, 1H, J = 1.5Hz). 13C-NMR (CDCl3, 50 MHz) d№ 14.5, 16.2, 20.1, 22.5, 23.1, 23.8, 30.8, 36.7, 37.0, 46.6, 59.3, 91.1, 92.1, 167.8, 181.3. IR (CCl4) : 1716, 1652, 1447 cm-1. Oxetane 27 (only one isomer observed) : colorless oil. 1H NMR (CDCl3, 200 MHz) : d№ 1.25 (t, 3H, J = 7.2Hz); 1.22-2.33 (m, 17H), 3.37 (ddd, J = 7.4, 3.5, 2.0 Hz), 4.10 (m, 2H), 5.10 (d, 1H, J = 2.0Hz). 13C-NMR (CDCl3, 50 MHz) d№ 14.5, 19.4, 22.7, 23.4, 22.7, 23.4, 27.5, 29.0, 30.2, 32.9, 39.1, 43.7, 49.4, 59.2, 90.4, 95.3, 167.9, 181.7. 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