ࡱ> ceb7 lbjbjUU 7|7|2GLlbbbvR R R 8  vF \ "~ ~ ~ ~ ~ ~ `bbbbbb$_ b~ ~ ~ ~ ~ n:6,~ ~ cnnn~ b~ b~ `n~ `nnbb~ : gT&vR \y0nnvvbbStereoselective 1,2-Additions of a-Alkoxymethyllithiums to Aldehydes Robert P. Smyj and J. Michael Chong Supporting Information General: All reactions were carried out with dry glassware under an atmosphere of argon unless otherwise noted. Tributyltinmethanol was prepared according to Seitz et al. 1-Bromo-3,3-dimethoxypropane (6), and (R)-isopropyloxirane (7), were also prepared according to literature procedures. Other reagents were purchased (Aldrich) or prepared by modification of literature methods. For 13C NMR signals, coupling constants for satellites due to 117/119Sn (where discernible) are reported. An asterisk (*) indicates signals that could be unequivocally attributed to the minor isomer in a mixture of diastereomers. Mass spectral data obtained by electron impact (EI) ionization were acquired by GC/MS analysis on a Hewlett Packard G1800A GCD system equipped with a HP-5 column (crosslinked 5% Ph Me silicone) (30 m x 0.25 mm x 0.25 mm film thickness). The GC retention times that are quoted were also obtained on the above GC/MS instrument and column with the following temperature program being employed: initial conditions: 50 C for 3 min, ramp: 15 C/min, final conditions: 220 C for 10 min. Elemental analyses were performed by M-H-W Laboratories, Phoenix, AZ. (S)-7,7-Dimethoxy-2-methylheptan-3-ol (8) This unreported compound was prepared by a procedure modified from that described by Johannsen. Mg turnings (2.19 g, 90 mmol) and 2 small crystals of I2 were heated under Ar for 2 min with stirring. The mixture was then allowed to cool to rt after which THF (20 mL) and 1,2-dibromoethane (0.52 mL, 6.0 mmol) were added. After initiation had taken place 1-bromo-3,3-dimethoxypropane (11 g, 60 mmol) in THF (80 mL) was added dropwise. The resulting Grignard solution was stirred at ambient temperature for 1 h. The mixture was then cooled to an internal temperature of -71 C and CuI (1.14 g, 6 mmol) was added and stirred for 15 min. (R)-Isopropyloxirane (7) (4.31 g, 50.0 mmol) was then added and the mixture was allowed to slowly reach rt and was stirred overnight. The reaction was then cooled (0 C) and slowly quenched with an aqueous 1.5% solution of NH4OH in saturated NH4Cl (pH 8 buffer) (50 mL) and stirred until all solid material had dissolved and bubbling had stopped. The layers were then separated and the aqueous layer was extracted with Et2O (3 x 100 mL). The combined organic extracts were then dried over anhydrous Na2SO4 and filtered. The filtrate was then concentrated in vacuo (rotary evaporator, bath temperature: 30 C) and the crude material was purified by silica gel chromatography (gradient elution: hexane to 15% to 30% to 50% Et2O in hexane) to afford 8.12 g of 8 (85% yield based on 7) as a colorless oil: GC retention time: 10.22 min; [a]D22 = - 19.2 (c = 0.60, CHCl3); IR (neat film) 3436 (O-H stretch), 2832, 1463, 1386, 1367, 1127 (C-O stretch), 1068 (C-O stretch), 982 (C-O stretch), 947 (C-O stretch), 839, 811 cm-1; 1H NMR (300 MHz, CDCl3) d 4.38 (t, 1H, J = 5.6 Hz, CH(OCH3)2), 3.24-3.42 (m, 1H, CH(OH)), 3.33 (s, 3H, OCH3), 3.32 (s, 3H, OCH3), 1.30-1.75 (m, 7H, 3 CH2 + CHCH3), 0.92 (d, 3H, J = 6.9 Hz, CH(CH3)(CH3)), 0.91 (d, 3H, J = 6.7 Hz, CH(CH3)(CH3)); 13C NMR (75.47 MHz, CDCl3) d 104.1 (CH(OCH3)2), 75.8 (CH(OH), 52.2 (OCH3), 52.1 (OCH3), 33.4 (CH2), 33.2 (CH2), 32.1 (CH2), 20.8 (CH), 18.5 (CH3), 17.0 (CH3); MS (EI) m/z 75 (100), 159 (M+ - OCH3, 2), 189 (M+ - 1, 0.1), 190 (M+, 0.02). Anal. Calcd for C10H22O3: C, 63.12; H, 11.65. Found: C, 62.88; H, 11.38. (S)-6-isopropyl-tetrahydro-pyran-2-ol (9) This compound has been reported in racemic form. A mixture of 8 (7.93 g, 41.7 mmol) and p-toluenesulfonic acid (793 mg, 4.17 mmol) in H2O/acetone (1:1) (200 mL) was stirred at rt for 1 h then refluxed for 1 h. A saturated solution of NaHCO3 was then added until the mixture was slightly basic by pH paper. The mixture was then extracted with Et2O (3 x 300 mL) followed by drying the combined organic extracts over anhydrous Na2SO4. The solution was then filtered and the filtrate was concentrated in vacuo. The crude material was purified by silica gel chromatography (gradient elution: hexane to 10% to 20% to 30% Et2O/hexane) to afford 4.83 g (69% yield) of 9 as a colorless oil and as an approximate 2:1 ratio of b:a anomers: GC retention time: 7.74 min (both isomers). Mutarotation was observed for 9, so that 5 min after a solution of 9 (c = 1.06, CHCl3) was made the following rotation was observed: [a]D22 = +52.4, which increased 2 min later to [a]D22 = +59.9. The rotation increased further over time and a steady reading ([a]D22 = +89.9) was obtained after 80 min from the time the solution was made. 1H NMR (200 MHz, CDCl3) d 5.27-5.38* (br m, 1H, anomeric-H), 4.61-4.76 (m, 1H, anomeric-H), 3.66* (ddd, 1H, J = 2.0, 6.3, 11.2 Hz, OCH(iPr)) 3.13 (ddd, 1H, J = 1.9, 6.4, 11.1 Hz, OCH(iPr)), 3.00 (d, 1H, J = 6.2 Hz, OH), 2.43* (dd, 1H, J = 1.7, 3.0 Hz, OH), 1.05-1.97 (m, 7H, 3 CH2 + CH(CH3)2), 0.96 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)), 0.92* (d, 3H, J = 6.7 Hz, CH(CH3)(CH3)), 0.91 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)), 0.88* (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)); 13C NMR (50.32 MHz, CDCl3) d 96.5 (anomeric-C), 91.6* (anomeric-C), 81.4 (OCH(iPr)), 73.3* (OCH(iPr)), 32.6 (CH2), 32.4* (CH2), 29.8 (CH2), 27.1* (CH2), 26.5 (CH2), 22.0 (CH(iPr)), 18.6 (CH(CH3)(CH3)), 18.4* (CH(CH3)(CH3)), 18.1* (CH(CH3)(CH3)), 17.8 (CH(CH3)(CH3)); MS (EI) m/z 55 (100), 101 (M+ - iPr, 69), 126 (M+ - H2O, 12), 143 (M+ - 1, 0.4), 144 (M+, 0.2). (S)-6-isopropyl-tetrahydro-pyran-2-one (10) This compound has been reported in racemic form and was prepared by a procedure modified from that described by Corey and Suggs. A mixture of lactol 9 (4.83 g, 33.5 mmol), PCC (14.8 g, 67.0 mmol), and crushed 4 molecular sieves (33 g) in CH2Cl2 (330 mL) was refluxed for 2.5 h. The reaction was then diluted with anhydrous Et2O (1 L) and filtered through Florisil. The filter cake was extracted with Et2O (4 x 300 mL) and the combined organic extracts were filtered once again through Florisil. The filtrate was then concentrated in vacuo and the crude material was purified by silica gel chromatography (gradient elution: 10% to 25% to 50% to 75% Et2O/hexane) to afford 3.77 g (79% yield) of 10 as a colorless oil: GC retention time: 9.49 min; [a]D22 = + 4.0 (c = 1.75, CHCl3); 1H NMR (300 MHz, CDCl3) d 4.06 (ddd, 1H, J = 2.9, 5.7, 11.3 Hz, (OCH(iPr)), 2.51-2.68 (m, 1H, CHHC=O), 2.35-2.50 (m, 1H, CHHC=O), 1.73-2.00 (m, 4H, CH2 + CHH + CH(CH3)2), 1.45-1.51 (m, 1H, CHH), 1.01 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)), 0.97 (d, 3H, J = 6.9 Hz, CH(CH3)(CH3)); 13C NMR d 172.0 (C=O), 85.1 (OCH(iPr)), 33.3 (CH2), 32.5 (CH2), 29.3 (CH2), 24.4 (CH(CH3)2), 17.7 (CH(CH3)(CH3), 17.5 (CH(CH3)(CH3); MS (EI) m/z 99 (M+ - iPr, 100), 142 (M+, 5). (S)-5-Hydroxy-6-methyl-1-phenylheptan-1-one (11) This compound has been reported in racemic form6 and was prepared as follows: To a cooled (-78 C) solution of lactone 10 (3.77 g, 26.5 mmol) in THF (265 mL) was added a 0.64 M solution of PhLi in Et2O, (43.5 mL, 27.8 mmol). The mixture was stirred for 30 min after which the reaction was quenched with a saturated aqueous solution of NH4Cl (30 mL). The mixture was then allowed to reach rt and the layers were separated. The aqueous layer was extracted with Et2O (3 x 50 mL) and the combined organic extracts were dried over anhydrous Na2SO4. The solution was then filtered and the filtrate was concentrated in vacuo. The crude material was then purified by silica gel chromatography (silica gel first deactivated with 1% Et3N/hexane)(gradient elution: 5% to 20% to 40% to 50% Et2O/hexane (all eluent contained 1% Et3N)) to afford 5.13 g of 3 (88% yield) as a colorless oil: [a]D22 = - 8.27 (c = 1.21, CHCl3); IR (neat film) 3436 (O-H stretch), 1682 (C=O stretch), 1449, 691 cm-1; 1H NMR (200 MHz, CDCl3) d 7.90-8.03 (m, 2H, Ar-H), 7.30-7.66 (m, 3H, Ar-H), 3.30-3.46 (br m, 1H, CH(OH)), 3.03 (t, 2H, J = 7.0 Hz, CH2C=O), 1.38-2.09 (m, 5H, 2 CH2 + CH(CH3)2), 0.92 (d, 6H, J = 6.8 Hz, CH(CH3)2); 13C NMR (50.32 MHz, CDCl3) d 200.4 (C=O), 136.8 (Ar-C), 132.8 (Ar-C), 128.4 (Ar-C), 127.9 (Ar-C), 76.1 (CHOH), 38.2 (CH2C=O), 33.4 (2 CH2), 20.5 (CH(CH3)2), 18.7 (CH(CH3)(CH3)), 17.1 (CH(CH3)(CH3)); MS (EI) 82 (100), 105 (90), 133 (71), 202 (M+ - H2O, 33), 203 (M+ - OH, 5). Tributyl([(2R,6S)-6-isopropyl-2-phenyltetrahydro-2H-2-pyranyl]oxymethyl)stannane (12) To a mixture of 11 (1.29 g, 5.86 mmol) and Bu3SnCH2OH (3.77 g, 11.73 mmol) in CH2Cl2 (120 mL) and in the presence of crushed 4 molecular sieves (23 g) was added camphorsulfonic acid (CSA) (1.09 g, 4.69 mmol). The mixture was stirred for 4 h after which the reaction was quenched with Et3N (2 mL) then filtered. The filtrate was then concentrated in vacuo. Since 12 is sensitive to acid, the crude material was quickly purified by silica gel chromatography (silica gel first deactivated with 0.1% Et3N/hexane)(gradient elution: hexane to 1% CH2Cl2/hexane (all eluent contained 0.1% Et3N)) to afford 2.03 g of compound 12 (66% yield) as a colorless oil: [a]D22 = + 58.9 (c = 1.06, CHCl3); IR (neat film) 2871, 2853, 1464, 1449, 1255, 1050 (C-O stretch), 1029 (C-O stretch), 1003 (C-O stretch), 864, 767, 753, 700 cm-1; 1H NMR (300 MHz, CDCl3) d 7.42-7.49 (m, 2H, Ar-H), 7.20-7.35 (m, 3H, Ar-H), 3.38-3.47 (m, 1H, OCH(iPr)), 3.42 (d, 1H, J = 10.1 Hz, 2JSn-H = 29.0 Hz, OCHHSnBu3), 2.99 (d, 1H, J = 10.2 Hz, 2JSn-H = 28.6 Hz, OCHHSnBu3), 1.86-2.03 (m, 2H, CCH2C), 1.79 (oct, 1H, J = 6.7 Hz, CH(CH3)), 1.19-1.67 (m, 16H, 2 CCH2C + Sn(CH2(CH2)2CH3)3), 1.05 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)), 1.00 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)), 0.70-0.98 (m, 15H, Sn(CH2(CH2)2CH3)3); 1H NMR (C6D6) d 7.68-7.78 (m, 2H, Ar-H), 7.24-7.35 (m, 2H, Ar-H), 7.05-7.20 (m ,1H, Ar-H), 3.69 (d, 1H, J = 10.3 Hz, 2JSn-H = 28.3 Hz, OCHHSnBu3), 3.58 (br dd, 1H, J = 6.1, 9.9 Hz, OCH(iPr)), 3.31 (d, 1H, J = 10.3 Hz, 2JSn-H = 28.6 Hz, OCHHSnBu3) 1.92-2.19 (m, 2H, CCH2C), 1.83 (oct, 1H, J = 6.6 Hz, CH(CH3)2), 1.22-1.71 (m, 16H, 2 CCH2C + Sn(CH2(CH2)2CH3)3), 1.17 (d, 3H, J = 6.7 Hz, CH(CH3)(CH3)), 0.78-1.09 (m, 15H, Sn(CH2(CH2)2CH3)3), 1.05 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)); 13C NMR (75.47 MHz, CDCl3) d 144.0 (Ar-C), 127.8 (Ar-C), 127.1 (Ar-C), 126.2 (Ar-C), 100.5 (3J = 45 Hz, anomeric-C), 74.8 (OCH(iPr), 49.6 (1J = 371, 388 Hz, OCH2SnBu3), 37.7 (CCH2C), 33.3 (CCH2C), 29.3 (2J = 21 Hz, Sn(CH2CH2CH2CH3)3), 27.4 (3J = 52 Hz, Sn(CH2)2CH2CH3)3, 27.2 (CCH2C), 19.8 (CH(CH3)2), 18.8 (CH(CH3)(CH3)), 18.4 (CH(CH3)(CH3)), 13.7 (Sn(CH2)3CH3)3, 8.9 (1J = 309, 323 Hz, Sn(CH2(CH2)2CH3)3); MS (FAB) m/z 105 (23), 145 (22), 203 (M+ - OCH2SnBu3, 100), 467 (M+ - C4H9, 2) Anal. Calcd for C27H48O2Sn: C, 61.97; H, 9.25. Found C, 61.78; H, 9.13. Transmetalation/trapping experiments with stannane 12 and formation of 2-[(2S,6S)-6-isopropyl-2-phenyltetrahydro-2H-2-pyranyl]oxy-1-phenyl-1-ethanol (13) All transmetalation/trapping experiments were carried out in a similar manner and a representative procedure follows: To a cooled solution (-78 (C) of 12 (112 mg, 0.214 mmol) in THF (4 mL) was added a solution of 1.57 M n-BuLi in hexane (0.28 mL, 0.440 mmol) dropwise and the resulting solution was stirred for 1 h. Benzaldehyde (65 mL, 0.639 mmol) was next added dropwise and the resulting solution was stirred for an additional 30 min, after which an aqueous solution of saturated NH4Cl (1 mL) was added. The aqueous layer was then separated and extracted with Et2O (2 x 15 mL). The combined organic layers were then dried over anhydrous Na2SO4, and concentrated in vacuo to obtain 178 mg of crude material. The addition adduct 13 is sensitive to acid, therefore purification of the crude material occurred by silica gel chromatography with deactivated silica gel (deactivated with 1% Et3N/hexane), employing gradient elution (all eluent containing 1% Et3N): (gradient elution: hexane to 5% to 10% to 15% to 20% Et2O/hexane) to obtain in order of elution: 67 mg (93% yield) of Bu4Sn, and a 70 mg mixture of unreported addition adduct 13 (58 mg, 80% yield, based on 12), and 1-phenyl-1-pentanol (12 mg, 17% yield, based on n-BuLi), (yields for 13 and 1-phenyl-1-pentanol determined by 1H NMR integration of benzylic-H) as a colourless oil. Furthermore, 13 was formed with 78:22 dr (dr determined by 1H NMR integration of benzylic-H). The following data was assigned to 13: GC retention time: 13.45 min; IR (neat film) 3436 (O-H stretch), 2873, 1449, 1249, 1027 (C-O stretch), 1012 (C-O stretch), 760, 700 cm-1; 1H NMR (200 MHz, CDCl3) d 7.17-7.56 (m, 5H, Ar-H), 4.83-4.96* (m, 1H, Bn-H), 4.71-4.81 (m, 1H, Bn-H), 3.25-3.54 (m, 2H, OCH(iPr) + OCHH), 2.94-3.20 (m, 1H, OCHH), 2.85 (br d, 1H, J = 2.5 Hz, OH), 2.74 (br s, 1H, OH), 1.13-2.17 (m, 7H, CCH2CH2CH2C + CH(CH3)2), 0.99 (d, 3H, J = 6.7 Hz, CH(CH3)(CH3)), 0.98* (d, 3H, J = 6.2 Hz, CH(CH3)(CH3)), 0.95 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)), 0.91* (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)); 13C NMR (75.47 MHz, CDCl3) d 143.4 (Ar-C), 143.3* (Ar-C), 140.7 (Ar-C), 128.2 (Ar-C), 128.0 (Ar-C), 127.6 (Ar-C), 126.0 (Ar-C), 125.5 (Ar-C), 99.4* (anomeric-C), 99.1 (anomeric-C), 75.2 (OCH), 74.7 (OCH), 73.3 (OCH), 73.1 (OCH), 66.3 (OCH2), 37.3 (CH(CH3)2), 33.4 (CCH2C), 32.8 (CCH2C), 27.1 (CCH2C), 19.7 (CCH2C), 19.2 (CCH2C), 19.0 (CH(CH3)(CH3)), 18.5 (CH(CH3)(CH3)), 18.4 (CH(CH3)(CH3)), 17.9 (CH(CH3)(CH3)); MS (EI) 55 (60), 77 (C6H5+, 49), 82 (100), 105 (72), 120 (49), 133 (44), 202 (M+ - HOCH2CH(OH)Ph, 21), 203 (M+ - OCH2CH(OH)Ph, 3). Recovery of (S)-1-phenyl-1,2-ethanediol (14) and auxiliary 11 The following procedure describes a representative transmetalation/trapping procedure (without purification of the addition adduct 13), followed by recovery of the auxiliary 11, and diol 14: To a cooled solution (-78 (C) of 12 (108 mg, 0.206 mmol) in THF (4 mL) was added a solution of 1.57 M n-BuLi in hexane (0.27 mL, 0.424 mmol) dropwise and the resulting solution was stirred for 1 h. Benzaldehyde (63 mL, 0.620 mmol) was next added dropwise and the resulting solution was stirred for an additional 30 min, after which an aqueous solution of saturated NH4Cl (1 mL) was added. The aqueous layer was then separated and extracted with Et2O (2 x 15 mL). The combined organic layers were then dried over anhydrous Na2SO4, and concentrated in vacuo to obtain 172 mg of crude material. The crude material containing the addition adduct 13 was then dissolved in MeOH (4 mL) and CSA (30 mg) was added. The mixture was stirred overnight at rt and the reaction was quenched with Et3N (1 mL). The solvent was then removed in vacuo. The crude material was purified by silica gel chromatography (gradient elution: hexane to 10% to 25% to 50% Et2O/hexane to neat Et2O to 10% MeOH/Et2O) to isolate 25.0 mg (55% yield based on 12) of auxiliary 11 (eluting in 50% Et2O/hexane) and 24.2 mg (85% yield based on 12) of diol 14 (eluting from neat Et2O to 10% MeOH/Et2O). The diol 14 was determined to be formed with 80:20 er (determined by chiral HPLC (elution: 5% iPrOH/hexane, 1.0 mL/min), on a Waters 600E instrument using a Waters 486 UV-visible detector at 254 nm, a Waters recording integrator, and a 4.6 mm x 150 mm Chiralcel OD column), with the S configuration present in the major isomer. Order of elution was determined using commercially available ()-14 (Aldrich # P2,405-5) and (R)-14 (Aldrich # 30,216-3). Retention times of 14: 19.80 min (R), 21.33 min (S). 1H NMR (250 MHz, CDCl3) d 7.25-7.45 (m, 5H, Ar-H), 4.79 (dd, 1H, J = 3.6, 8.0 Hz, Bn-H), 3.55-3.80 (m, 2H, CH2OH), 2.85 (br s, 2H, OH). Recovery of the auxiliary as the methyl glycoside 17 Another representative procedure follows, which includes the recovery of the auxiliary as the methyl glycoside 17, followed by characterization data for unreported compound 17: To a cooled solution (-78 (C) of 12 (110 mg, 0.210 mmol) in THF (1.42 mL) and Et2O (3.32 mL) (i.e. 30% THF in Et2O) was added a solution of 1.51 M n-BuLi in hexane (0.28 mL, 0.420 mmol) dropwise and the resulting solution was stirred for 1 h. Benzaldehyde (64 mL, 0.630 mmol) was next added dropwise and the resulting solution was stirred for an additional 30 min, after which an aqueous solution of saturated NH4Cl (1 mL) was added. The aqueous layer was then separated and extracted with Et2O (2 x 15 mL). The combined organic layers were then dried over anhydrous Na2SO4, and concentrated in vacuo. The crude material containing the addition adduct 13 was then dissolved in MeOH (4 mL) and CSA (30 mg) was added. The mixture was stirred overnight at rt and the reaction was quenched with Et3N (1 mL). The solvent was then removed in vacuo. Compound 17 is sensitive to acid; therefore purification of the crude material was performed with deactivated silica gel (1% Et3N/hexane), employing gradient elution (all eluent containing 1% Et3N): hexane to 1% to 2% CH2Cl2/hexane to isolate 44.9 mg (91% yield) of recovered methyl glycoside auxiliary 17, followed by elution with 10% to 25% to 50% Et2O/hexane to neat Et2O to 10% MeOH/Et2O to isolate 26.4 mg (91% yield) of diol 16 (88:12 er, major S). (6S)-6-isopropyl-2-methoxy-2-phenyltetrahydro-2H-pyran (17)  EMBED ChemDraw.Document.5.0  The following data was obtained for unreported compound 17: [a]D22 = + 62.3 (c = 0.58, CHCl3); IR (neat film) 2872, 2829, 1494, 1256, 1155 (C-O stretch), 1039 (C-O stretch), 1015 (C-O stretch), 866, 762, 700 cm-1; 1H NMR (300MHz, CDCl3) d 7.45-7.55 (m, 2H, Ar-H), 7.23-7.38 (m, 3H, Ar-H), 3.49 (ddd, 1H, J = 2.1, 6.0, 11.6 Hz, OCH(iPr)), 2.97 (s, 3H, OCH3), 1.88-2.06 (m, 2H, CCH2C), 1.79 (oct, 1H, J = 6.7 Hz, CH(CH3)2), 1.60-1.75 (m, 2H, CCH2C), 1.21-1.52 (m, 2H, CCH2C), 1.05 (d, 3H, J = 6.7 Hz, CH(CH3)(CH3)), 1.00 (d, 3H, J = 6.8 Hz, CH(CH3)(CH3)); 13C NMR (75.47 MHz, CDCl3) d 143.7 (Ar-C), 128.0 (Ar-C), 127.4 (Ar-C), 125.9 (Ar-C), 99.4 (anomeric-C), 74.9 (OCH), 48.8 (OCH3), 37.5 (CCH2C), 33.2 (CCH2C), 27.2 (CCH2C), 19.7 (CH(CH3)2), 18.8 (CH(CH3)(CH3)), 18.2 (CH(CH3)(CH3)); MS (EI) m/z 105 (100), 133 (60), 191 (M+ - CH(CH3)2, 0.1), 202 (M+ - CH3OH, 38), 203 (M+ - CH3O, 7), 233 (M+ - 1, 0.03), 234 (M+, 0.05), 235 (M+ + 1, 0.07); HRMS (FAB) calcd for C15H22O2 234.1620, found 234.1632. References: PAGE  PAGE 12  Seitz, D. E.; Carroll, J. J.; Cartaya, M. C. P.; Lee, S.-H.; Zapata, A. Synthetic Commun. 1983, 13, 2, 129-134.  Lee, T. V.; Porter, J. R. Organic Syntheses; volume 72; Coffen, D. L., Ed.; John Wiley & Sons: New York, 1994; pp. 189-198.  Koppenhoefer, B.; Schurig, V. Organic Syntheses; volume 66; Heathcock, C. H., Ed.; John Wiley & Sons: New York, 1988; pp.160-172.  Johannsen, J. A. M.Sc. Dissertation, University of Waterloo, Waterloo, ON, 1994, p.195.  Ramon, D. J.; Yus, M. Tetrahedron Lett. 1990, 31, 3767-3770.  Warnhoff, E. W.; Wong, M. Y. H.; Raman, P. S. Can. J. Chem. 1981, 59, 688-696.  Corey, E. J.; Suggs, J. W. Tetrahedron Lett. 1975, 2647-2650.  Wakefield, B. J. Organolithium Methods; Academic Press: London, 1988; p. 24.  Burchat, A. F.; Chong, J. M.; Nielsen, N. J. Organomet. Chem. 1997, 542, 281-283. 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