2-ethenyloxirane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the general procedure of Example 13A, 5-hexenol was added to butadiene monoepoxide, using the following quantities of reagents and solvents: Pd2dba3.CHCl3 (5.2 mg, 5.0 μmol), (±)-8 (10.4 mg, 15 μmol), DMAP (6.2 mg, 50 μmol), a 1.0 M solution of Et3B in THF (5.0 μL, 5.0 μmol), 5-hexenol (240 μL, 2.0 mmol), butadiene monoepoxide (81 μL, 1.0 μmol), CH2Cl2 (10 mL). The reaction time in this case was 4 h. Flash chromatography of the crude material (silica gel, 4:1 pentane-ether) afforded ˜135 mg (80%) of a colorless oil. (enantiomers separated by chiral GLC, Cyclosil B column isothermal 120° C, (S)-(+)-isomerrt=15.52 min, (R)-(−)-isomerrt=16.21 min). 1H NMR (300 MHz) δ 1.36-1.43 (m, 2H), 1.50-1.58 (m, 2H), 1.97-2.04 (m, 2H), 2.50 (br s, 1H), 3.24-3.31 (m, 1H), 3.43-3.53 (m, 3H), 3.71-3.75 (m,1H), 4.89 (d, 1H, J=11 Hz), 4.94 (d, 1H, J=19Hz), 5.20 (d, 1H, J=9 Hz), 5.24 (d, 1H, J=17 Hz), 5.57-5.78 (m, 2H); 13C NMR (75.5 MHz) δ 25.3, 29.1, 33.4, 65.1, 68.6, 81.6, 114.5, 118.4, 135.4, 138.5. Anal. Calc'd. for C10H18O2: C, 70.55; H, 10.66. Found: C, 70.66; H, 10.43.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Following the general procedure in Example 13A, 4-pentenol was added to butadiene monoepoxide, using the following quantities of reagents and solvents: Pd2dba3.CHCl3 (5.2 mg, 5.0 μmol), (S,S)-9 (11.8 mg, 15 μmol), DMAP (6.2 mg, 50 μmol), a 1.0 M solution of Et3B in THF (5.0 μL, 5.0 μmol), 4-pentenol (207 μL, 2.0 mmol), butadiene monoepoxide (81 μL, 1.0 mmol), CH2Cl2 (10 mL). The reaction time in this case was 4 h. Flash chromatography of the crude material (silica gel, 4:1 pentane-ether) afforded 131 mg (84%) of a colorless oil in 90% ee (separated by chiral GLC, Cyclosil B column, isothermal 120° C., (S)-(+)-isomerrt=9.33 min, (R)-(−)-isomerrt=9.68 min). [α]D=−33.2° (c 2.86, CHCl3); 1H NMR (300 MHz) δ 1.66 (quint 2H, J=7 Hz), 2.07-2.26 (m, 3H), 3.28-3.61 (m, 4H), 3.75-3.81 (m, 1H), 4.94 (d, 1H, J=11 Hz), 5.00 (d, 1H, J=17 Hz), 5.24 (d, 1H, J=9 Hz), 5.28 (d, 1H, J=17 Hz), 5.60-5.83 (m, 2H). 13C NMR (75.5 MHz) δ 28.9, 30.4, 65.2, 68.2, 81.6, 114.8, 118.7, 135.4, 138.2. Anal. Calc'd. for C9H16O2: C, 69.19; H, 10.32. Found: C, 69.23; H, 10.14.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To an oven dried test tube was added Pd2dba3.CHCl3 (5.2 mg, 5.0 μmol), chiral ligand (S,S)-9 (11.8 mg, 15 μmol), DMAP (6.2 mg, 50 μmol) and a stirbar. Several drops of CH2Cl2 were then added to wet the catalyst, and the test tube was immediately placed under reduced pressure (vacuum pump) for 10 sec and refilled with Ar. This purging procedure was repeated five times to ensure no oxygen remained in the reaction vessel. After being placed under an Ar atmosphere, freshly distilled and degassed methylene chloride was added (10 mL) and the resulting dark purple mixture was stirred at room temperature until it turned a deep orange color (roughly 15 min). During this time, the 3-butenol (172 μL, 2.0 μmol) and a 1.0 M solution of Et3B in THF was added (5.0 μL, 5.0 μmol). To the solution of catalyst and alcohol was added neat butadiene monoepoxide (81 μL, 1.0 μmol) and the solution immediately turned pale yellow. Stirring was continued for 4 h. The solvent was removed in vacuo. Flash chromatography of the crude material (silica gel, 4:1 pentane-ether) afforded 116 mg (82%) of 27 as a colorless oil in 90% ee (separated by chiral GLC, Cyclosil B column, isothermal 100° C., (S)-(+)-isomerrt=11.97 min, (R)-(−)-isomerrt=12.20 min). [α]D=−50.0° (c 2.20, CHCl3); 1H NMR (300 MHz): δ 2.09 (br s, 1H), 2.28-2.35 (m, 2H), 3.32-3.40 (m, 1H), 3.46-3.66 (m, 3H), 3.77-3.83 (m, 1H), 5.01 (d, IH, J=11 Hz), 5.10 (d, 1H, J=17 Hz), 5.23 (d, 1H, J=10 Hz), 5.28 (d, 1H, J=17 Hz), 5.60-5.84 (m, 2H); 13C NMR (75 MHz): δ 34.2, 65.3, 67.9, 81.7, 116.6, 118.7, 135.2, 135.2. Anal. Calcd. for C8H14O2: C, 67.57; H, 9.92; found C, 67.36; H, 9.80. To an oven dried test tube was added Pd2dba3 refilled with Ar freshly distilled degassed methylene chloride was added (10 mL) a deep orange color (roughly 15 min) Stirring was continued for 4 h The solvent was removed in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: oxocane; 2,3-epoxybutane; 1,2-epoxybut-3-ene; styrene oxide; 2-ethylfuran; 2-tert-butylfuran; 2,3-dimethylfuran; 2,3-dihydrobenzofuran; dimethyl 3-furylmethyl borate; 2-trimethylsilylfuran; 3-trimethylsilylfuran; oxazole; 1,3,4-oxadiazole; 3,4-dichloro-1,2-epoxybutane; 3,4-dibromo-1,2-epoxybutane and the like.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CPCA is derived from 1,3-butadiene by a sequence of four reactions. Monoepoxidation of 1,3-butadiene produces 3,4-epoxy-1-butene (EPB) as described in U.S. Pat. Nos. 4,897,498 and 4,950,773. This epoxide is isomerized to 2,5-DHF (U.S. Pat. Nos. 5,082,956 and 5,315,019) which is isomerized to 2,3-DHF (U.S. Pat. Nos. 5,254,701 and 5,536,851). Finally, 2,3-DHF is isomerized to CPCA (C. L. Wilson, J. Amer. Chem. Soc., 69, 3002 (1947) and U.S. Pat. No. 5,502,257).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: CPCA is derived from 1,3-butadiene by a sequence of four reactions. Monoepoxidation of 1,3-butadiene produces 3,4-epoxy-1-butene (EPB) as described in U.S. Pat. Nos. 4,897,498 and 4,950,773. This epoxide is isomerized to 2,5-DHF (U.S. Pat. Nos. 5,082,956 and 5,315,019) which is isomerized to 2,3-DHF (U.S. Pat. Nos. 5,254,701 and 5,536,851). Finally, 2,3-DHF is isomerized to CPCA (C. L. Wilson, J. Amer. Chem. Soc., 69, 3002 (1947) and U.S. Pat. No. 5,502,257).

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A quantity of CuCN, 2.43 g, was added to a solution of butadiene monooxide, 19 g, in 500 mL anhydrous tetrahydrofuran and the mixture was cooled to -78° C. Phenyl magnesium bromide solution in ether, 32 mmol, was added dropwise to this mixture. The reaction mixture was warmed to 0° C. and was stirred until the reaction became homogeneous. The reaction mixture was cooled to -78° C. and 0.29 mole of phenylmagnesium bromide solution in ether was added dropwise for 30 min. The reaction mixture was allowed to warm to room temperature with stirring then quenched by slow addition of saturated NH4Cl (50 mL) followed by NH4OH (30 mL), saturated NH4Cl (200 mL) and H2O (100 mL). Aqueous layer was extracted with two 200 mL portions of ethyl acetate. Combined organic layers were dried and concentrated. The residue was distilled under vacuum (0.1 torr) at 100° C. to give trans-4-phenyl-2-butene-1-ol (38.9 g, 79% pure). The reaction mixture was warmed to 0° C. The reaction mixture was cooled to -78° C. to warm to room temperature with stirring then quenched by slow addition of saturated NH4Cl (50 mL) Aqueous layer was extracted with two 200 mL portions of ethyl acetate Combined organic layers were dried concentrated The residue was distilled under vacuum (0.1 torr) at 100° C.

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A quantity of CuCN, 2.43 g, was added to a solution of butadiene monooxide, 19 g, in 500 mL anhydrous tetrahydrofuran and the mixture was cooled to -78° C. Phenyl magnesium bromide solution in ether, 32 mmol, was added dropwise to this mixture. The reaction mixture was warmed to 0° C. and was stirred until the reaction became homogeneous. The reaction mixture was cooled to -78° C. and 0.29 mole of phenylmagnesium bromide solution in ether was added dropwise for 30 min. The reaction mixture was allowed to warm to room temperature with stirring then quenched by slow addition of saturated NH4Cl (50 mL) followed by NH4OH (30 mL), saturated NH4Cl (200 mL) and H2O (100 mL). Aqueous layer was extracted with two 200 mL portions of ethyl acetate. Combined organic layers were dried and concentrated. The residue was distilled under vacuum (0.1 torr) at 100° C. to give trans-4-phenyl-2-butene-1-ol (38.9 g, 79% pure). The reaction mixture was warmed to 0° C. The reaction mixture was cooled to -78° C. to warm to room temperature with stirring then quenched by slow addition of saturated NH4Cl (50 mL) Aqueous layer was extracted with two 200 mL portions of ethyl acetate Combined organic layers were dried concentrated The residue was distilled under vacuum (0.1 torr) at 100° C.

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 258 mg of TMEDA in 1 ml of hexane was cooled to 0° C., and a hexane solution of n-butyllithium (1.1 mmol) was added dropwise thereto under a nitrogen atmosphere and stirred at 0° C. To the resultant mixture, there was added dropwise 1 ml of a hexane solution of 3,4-epoxy-butene-1 (1 mol/liter). After completion of the addition, the resultant mixture was stirred at 0° C. for 1 hour and at room temperature for 30 minutes, followed by the usual work up. After removal of the solvent, the residue was distilled to give 41 mg of 2-octen-1-ol as a colorless oily product (yield, 32%). After acetylation of the thus obtained product, gas chromatographic analysis (PEG 20M, 45 m) was effected at a temperature of 130° C. The Z/E ratio was 76.8/23.2. After completion of the addition After removal of the solvent the residue was distilled

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 258 mg of TMEDA in 1 ml of hexane was cooled to 0° C., and a hexane solution of n-butyllithium (1.1 mmol) was added dropwise thereto under a nitrogen atmosphere and stirred at 0° C. To the resultant mixture, there was added dropwise 1 ml of a hexane solution of 3,4-epoxy-butene-1 (1 mol/liter). After completion of the addition, the resultant mixture was stirred at 0° C. for 1 hour and at room temperature for 30 minutes, followed by the usual work up. After removal of the solvent, the residue was distilled to give 41 mg of 2-octen-1-ol as a colorless oily product (yield, 32%). After acetylation of the thus obtained product, gas chromatographic analysis (PEG 20M, 45 m) was effected at a temperature of 130° C. The Z/E ratio was 76.8/23.2. After completion of the addition After removal of the solvent the residue was distilled

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A hexane solution of n-butyllithium (2.1 mmol) was cooled at 0° C. under the argon atmosphere. A hexane solution of n-butanol (75.9 mg; 1.0 mmol) was added dropwise thereto and stirred. To the resulting solution, there was further added dropwise a hexane solution of 3,4-epoxy-butene-1 (70.0 mg; 1 mmol), and after the addition was completed, the resulting mixture was cooled at 0° C. for 1 hour and at room temperature for 30 minutes, followed by the usual work up. Removal of the solvent and distillation of the residue gave 63 mg of 2-octen-1-ol (yield, 49%). After acetylation of the thus obtained product, gas chromatographic analysis (PEG 20M, 4 m) was effected at a temperature of 130° C. The retention times of Z-isomer and E-isomer were respectively 13.7 minutes and 14.7 minutes, and the Z/E ratio was 89.1/10.9. after the addition Removal of the solvent and distillation of the residue

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Concentrated sulfuric acid (18M; 0.1 mL; 2 mmol; 0.02 equiv.) was added to 80 mL of tert-butanol. Butadiene monoepoxide (8.05 mL; 100 mmol) was added and the reaction mixture was heated to reflux overnight (15 h) to completely consume butadiene monoepoxide by GC analysis. The reaction mixture was concentrated at reduced pressure and the residue was dissolved in ether (40 mL) and washed with saturated aqueous NaHCO3 (2×10 mL). The organic solution was dried (MgSO4) and concentrated, and the crude product was fractionated in vacuo, affording pure 1j (3.12 g; 22%), bp 42°-45°/1 mm Hg along with an impure fraction, 3.83 g, bp 45°-85°/1 mm Hg. 1H nmr (300 MHz, CDCl3): 5.797 (1H, ddd, J=6.29, 10.57, 17.07 Hz); 5.260 (1H, d, J=17.22 Hz); 5.144 (1H, d, J=10.50 Hz); 4.092 (1H, br q, J=5.76 Hz); 3.469 (1H, dd, J=4.45, 11.07 Hz); 3.399 (1H, dd, J=7.63, 11.14 Hz); 2.0 (1H, br s); 1.218 (9H, s). the reaction mixture was heated The reaction mixture was concentrated at reduced pressure the residue was dissolved in ether (40 mL) washed with saturated aqueous NaHCO3 (2×10 mL) The organic solution was dried (MgSO4) concentrated