oct-4-en-3-one

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

Procedure: A 500 ml flask was charged with 100.0 g of prenyl mesityl oxide (13% nonconjugated 79.7% conjugated isomer), 0.56 mole, 40.6 g ethylene diamine, and 0.5 g NaOH. This was then flushed thoroughly with nitrogen. The mixture was heated at between 95° and 105° C. and agitated for approximately four hours under a slight nitrogen pressure. Analysis by gas liquid chromatography indicated that 31.9% prenyl mesityl oxide remained unchanged after this time. Steam distillation of the pot mixture gave a true yield of 95.8% of methyl heptenone based on the prenyl mesityl oxide reacted, after the recovery of unreacted prenyl mesityl oxide. This was then flushed thoroughly with nitrogen The mixture was heated at between 95° and 105° C. Steam distillation of the pot mixture

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

Procedure: A 500 ml flask was charged with 100.0 g of prenyl mesityl oxide (13% nonconjugated 79.7% conjugated isomer), 0.56 mole, 40.6 g ethylene diamine, and 0.5 g NaOH. This was then flushed thoroughly with nitrogen. The mixture was heated at between 95° and 105° C. and agitated for approximately four hours under a slight nitrogen pressure. Analysis by gas liquid chromatography indicated that 31.9% prenyl mesityl oxide remained unchanged after this time. Steam distillation of the pot mixture gave a true yield of 95.8% of methyl heptenone based on the prenyl mesityl oxide reacted, after the recovery of unreacted prenyl mesityl oxide. This was then flushed thoroughly with nitrogen The mixture was heated at between 95° and 105° C. Steam distillation of the pot mixture

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

Procedure: Prepared according to general procedure A from oct-4-en-3-one (112 μL, 0.75 mmol), cyclopentadiene (93 μL, 1.13 mmol), 70% aqueous perchloric acid (12.9 μL, 0.15 mmol) and (2S, 5S)-5-benzyl-3-methyl-2-(5-methyl-furan-2-yl)-imidazolidin-4-one (40.5 mg, 0.15 mmol) in water (150 μL) for 32 hours at 0° C. Purification by silica gel chromatography (15:1 pentane:ether) provided the title compound as a colorless oil in 84% yield (120 mg, 0.62 mmol); 15:1 endo:exo, endo 92% ee. IR (film) 3060, 2961, 2872, 1710, 1459, 1413, 1377, 1333, 1216, 1106, 1017, 935.7, 904.3, 716.7 cm−1; 1H NMR (300 MHz, CDCl3) δ 6.22 (dd, J=6.0, 3.3 Hz, 1H, CH═CH), 5.84 (dd,J=5.4, 2.7 Hz, 1H, CH═CH), 3.12 (m, 1H, CHCH═CH), 2.57 (m, 1H, CHCH═CH), 2.45 (m, 3H, CH2CO and CHCO), 1.83 (m, 1H, CH(nPr)), 1.59-1.19 (br m, 6H, CH3CH2CH2, and CHCH2CH), 1.02 (dd, J=6.0, 6.0 Hz, 3H, CH3), 0.89 (dd, J=7.2, 7.2 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3) δ 211.7, 138.8, 132.4, 59.5, 47.3, 47.2, 46.6, 41.4, 38.7, 35.1, 22.3, 14.7, 8.3; HRMS (CI) exact mass calc'd for (CH13H20O) requires m/z 192.1514, found m/z 192.1512. [α]D=+91.5 (c=1.0, CHCl3). Product ratios were determined by GLC analysis (150° C., 23 psi); (1R, 2R, 3S, 4R) endo isomer tr=6.0 min, and (1S, 2S, 3R, 4S) endo isomer tr=5.6 min, exo isomers tr=5.1, 5.4 min. Prepared Purification by silica gel chromatography (15:1 pentane:ether)

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

Procedure: A 500 ml flask was charged with 100.0 g of prenyl mesityl oxide (13% nonconjugated 79.7% conjugated isomer), 0.56 mole, 40.6 g ethylene diamine, and 0.5 g NaOH. This was then flushed thoroughly with nitrogen. The mixture was heated at between 95° and 105° C. and agitated for approximately four hours under a slight nitrogen pressure. Analysis by gas liquid chromatography indicated that 31.9% prenyl mesityl oxide remained unchanged after this time. Steam distillation of the pot mixture gave a true yield of 95.8% of methyl heptenone based on the prenyl mesityl oxide reacted, after the recovery of unreacted prenyl mesityl oxide. This was then flushed thoroughly with nitrogen The mixture was heated at between 95° and 105° C. Steam distillation of the pot mixture

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

Procedure: By using the same reaction vessel as used in Example 1, 10.45 g of prenyl chloride, 34.8 ml of acetone, 20.3 g of a 65 % aqueous caustic soda solution, 5 ml of n-decane and 0.264 g of lauryl trimethylammonium chloride were added into the vessel, and then the mixture was allowed to react for 12 hours at 30°C. with vigorous stirring. After the reaction was completed, 40 ml of water was added to the resultant solution to dissolve the sodium chloride. Methyl heptenone was produced as determined by using gas chromatography and the yield was 51 % calculated on the theoretical value. were added into the vessel to react for 12 hours at 30°C. with vigorous stirring

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

Procedure: Acetone under the reaction conditions forms mesityl oxide, and this then reacts with the prenyl chloride to produce the above isomers; in the same manner, acetone reacts with prenyl chloride to produce methyl heptenone. to produce the above isomers

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

Procedure: Prepared according to general procedure A from oct-4-en-3-one (112 μL, 0.75 mmol), cyclopentadiene (93 μL, 1.13 mmol), 70% aqueous perchloric acid (12.9 μL, 0.15 mmol) and (2S, 5S)-5-benzyl-3-methyl-2-(5-methyl-furan-2-yl)-imidazolidin-4-one (40.5 mg, 0.15 mmol) in water (150 μL) for 32 hours at 0° C. Purification by silica gel chromatography (15:1 pentane:ether) provided the title compound as a colorless oil in 84% yield (120 mg, 0.62 mmol); 15:1 endo:exo, endo 92% ee. IR (film) 3060, 2961, 2872, 1710, 1459, 1413, 1377, 1333, 1216, 1106, 1017, 935.7, 904.3, 716.7 cm−1; 1H NMR (300 MHz, CDCl3) δ 6.22 (dd, J=6.0, 3.3 Hz, 1H, CH═CH), 5.84 (dd,J=5.4, 2.7 Hz, 1H, CH═CH), 3.12 (m, 1H, CHCH═CH), 2.57 (m, 1H, CHCH═CH), 2.45 (m, 3H, CH2CO and CHCO), 1.83 (m, 1H, CH(nPr)), 1.59-1.19 (br m, 6H, CH3CH2CH2, and CHCH2CH), 1.02 (dd, J=6.0, 6.0 Hz, 3H, CH3), 0.89 (dd, J=7.2, 7.2 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3) δ 211.7, 138.8, 132.4, 59.5, 47.3, 47.2, 46.6, 41.4, 38.7, 35.1, 22.3, 14.7, 8.3; HRMS (CI) exact mass calc'd for (CH13H20O) requires m/z 192.1514, found m/z 192.1512. [α]D=+91.5 (c=1.0, CHCl3). Product ratios were determined by GLC analysis (150° C., 23 psi); (1R, 2R, 3S, 4R) endo isomer tr=6.0 min, and (1S, 2S, 3R, 4S) endo isomer tr=5.6 min, exo isomers tr=5.1, 5.4 min. Prepared Purification by silica gel chromatography (15:1 pentane:ether)

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

Procedure: A 500 ml flask was charged with 100.0 g of prenyl mesityl oxide (13% nonconjugated 79.7% conjugated isomer), 0.56 mole, 40.6 g ethylene diamine, and 0.5 g NaOH. This was then flushed thoroughly with nitrogen. The mixture was heated at between 95° and 105° C. and agitated for approximately four hours under a slight nitrogen pressure. Analysis by gas liquid chromatography indicated that 31.9% prenyl mesityl oxide remained unchanged after this time. Steam distillation of the pot mixture gave a true yield of 95.8% of methyl heptenone based on the prenyl mesityl oxide reacted, after the recovery of unreacted prenyl mesityl oxide. This was then flushed thoroughly with nitrogen The mixture was heated at between 95° and 105° C. Steam distillation of the pot mixture