3-methylcyclopentadecan-1-one

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

Procedure: Mixed in 20 mL of a phosphate buffer (pH 7) were 2.0 g of dl-3-methylcyclopentadecene-1-yl acetate as obtained in Example 1 (a) and 1.0 g (50 wt. % relative to the substrate) of the immobilized enzyme (Novozyme 435) originating from Candida antarctica, followed by vigorous shaking at 55° C. for 2 days. After the reaction, 20 mL of hexane was added to the reaction solution for extraction, and analysis of the hexane layer showed that the conversion of the substrate was 69.8% and that 3-methylcyclopentadecanone was produced, while 3-methylcyclopentadecene-1-yl acetate remained. The hexane solution was purified by silica-gel column chromatography, and 3-methylcyclopentadecanone, as produced by hydrolyzing a portion of the remained 3-methylcyclopentadecene-1-yl acetate by the conventional method, was subjected to determination of the optical purity by HPLC and identified as the (S) isomer with 90.8% ee of optical purity. Also, 3-methylcyclopentadecanone, a enzymatic hydrolysate of the substrate, was subjected to determination of the optical purity and identified as the (R) isomer with 42.6% ee of optical purity. The hexane solution was purified by silica-gel column chromatography, and 3-methylcyclopentadecanone as produced

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Mixed in 20 mL of a phosphate buffer (pH 7) were 2.0 g of dl-3-methylcyclopentadecene-1-yl acetate as obtained in Example 1 (a) and 1.0 g (50 wt. % relative to the substrate) of the immobilized enzyme (Novozyme 435) originating from Candida antarctica, followed by vigorous shaking at 55° C. for 2 days. After the reaction, 20 mL of hexane was added to the reaction solution for extraction, and analysis of the hexane layer showed that the conversion of the substrate was 69.8% and that 3-methylcyclopentadecanone was produced, while 3-methylcyclopentadecene-1-yl acetate remained. The hexane solution was purified by silica-gel column chromatography, and 3-methylcyclopentadecanone, as produced by hydrolyzing a portion of the remained 3-methylcyclopentadecene-1-yl acetate by the conventional method, was subjected to determination of the optical purity by HPLC and identified as the (S) isomer with 90.8% ee of optical purity. Also, 3-methylcyclopentadecanone, a enzymatic hydrolysate of the substrate, was subjected to determination of the optical purity and identified as the (R) isomer with 42.6% ee of optical purity.

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Mixed in 20 mL of a phosphate buffer (pH 7) were 2.0 g of dl-3-methylcyclopentadecene-1-yl acetate as obtained in Example 1 (a) and 1.0 g (50 wt. % relative to the substrate) of the immobilized enzyme (Novozyme 435) originating from Candida antarctica, followed by vigorous shaking at 55° C. for 2 days. After the reaction, 20 mL of hexane was added to the reaction solution for extraction, and analysis of the hexane layer showed that the conversion of the substrate was 69.8% and that 3-methylcyclopentadecanone was produced, while 3-methylcyclopentadecene-1-yl acetate remained. The hexane solution was purified by silica-gel column chromatography, and 3-methylcyclopentadecanone, as produced by hydrolyzing a portion of the remained 3-methylcyclopentadecene-1-yl acetate by the conventional method, was subjected to determination of the optical purity by HPLC and identified as the (S) isomer with 90.8% ee of optical purity. Also, 3-methylcyclopentadecanone, a enzymatic hydrolysate of the substrate, was subjected to determination of the optical purity and identified as the (R) isomer with 42.6% ee of optical purity.

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Mixed in 20 mL of a phosphate buffer (pH 7) were 2.0 g of dl-3-methylcyclopentadecene-1-yl acetate as obtained in Example 1 (a) and 1.0 g (50 wt. % relative to the substrate) of the immobilized enzyme (Novozyme 435) originating from Candida antarctica, followed by vigorous shaking at 55° C. for 2 days. After the reaction, 20 mL of hexane was added to the reaction solution for extraction, and analysis of the hexane layer showed that the conversion of the substrate was 69.8% and that 3-methylcyclopentadecanone was produced, while 3-methylcyclopentadecene-1-yl acetate remained. The hexane solution was purified by silica-gel column chromatography, and 3-methylcyclopentadecanone, as produced by hydrolyzing a portion of the remained 3-methylcyclopentadecene-1-yl acetate by the conventional method, was subjected to determination of the optical purity by HPLC and identified as the (S) isomer with 90.8% ee of optical purity. Also, 3-methylcyclopentadecanone, a enzymatic hydrolysate of the substrate, was subjected to determination of the optical purity and identified as the (R) isomer with 42.6% ee of optical purity.

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

Procedure: In 10 ml of dried toluene was dissolved 5 mmol of (E)-2-cyclopentadecenone, and the solution was added dropwise to the above solution, followed by allowing the reaction to proceed at -78° C. to -60° C. for 15 hours. Thereafter, the same procedures as in Example 14 were followed to obtain muscone having an optical rotation of +11.8° (at 21° C., c 5.13, MeOH) and an optical purity of 100 %ee in a chemical yield of 90 mol %. the solution was added dropwise to the above solution the reaction

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

Procedure: In 10 ml of dried toluene was dissolved 5 mmol of (E)-2-cyclopentadecenone, and the solution was added dropwise to the above solution, followed by allowing the reaction to proceed at a temperature from -78° C. to -60° C. for 15 hours. Thereafter, the same procedures as in Example 14 were followed to obtain muscone in a chemical yield of 89 mol %. The resulting muscone was R-form having an optical rotation of -12.0° (at 21° C., c 5.07, MeOH) and an optical purity of 100%ee. the solution was added dropwise to the above solution the reaction

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

Procedure: In 10 ml of dried diethyl ether was dissolved 5 mmol of (E)-2-cyclopentadecenone, and the solution was added dropwise to the above solution at -78° C. The mixture was allowed to react at that temperature for 15 hours, and 12 ml of a 1:1 (by volume) mixture of aqueous ammonia and a saturated ammonium chloride aqueous solution was added thereto. The reaction mixture was extracted with diethyl ether, and the extracted product was purified by silica gel column chromatography using hexane/ethyl acetate (45:1 by volume) to obtain muscone in a chemical yield of 57 mol %. The resulting muscone was R-form having an optical rotation of -11.6° (at 21° C., c 5.03, MeOH) and an optical purity of 99%ee. the solution was added dropwise to the above solution at -78° C to react at that temperature for 15 hours The reaction mixture was extracted with diethyl ether the extracted product was purified by silica gel column chromatography

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

Procedure: The solution was cooled to -78° C., and a solution of 0.3604 g (1.62 mmol) of 2-cyclopentadecenone in 1 ml of toluene was added thereto dropwise, followed by stirring at -78° C. for 17 hours. To the reaction mixture was added 4 ml of a 1:1 (by volume) mixture of aqueous ammonia and a saturated ammonium chloride aqueous solution, followed by heating up to room temperature. The aqueous layer was removed, and the organic layer was washed successively with a 1:1 (by volume) mixture of aqueous ammonia and a saturated ammonium chloride aqueous solution, a 5% hydrochloric acid aqueous solution, a saturated sodium chloride aqueous solution, and a saturated sodium carbonate aqueous solution, and dried over sodium sulfate. The toluene was removed by distillation, and the residue was purified by silica gel column chromatography using hexane/ethyl acetate (40:1 by volume) as an eluent and then distilled under reduced pressure to obtain an optically active muscone. The yield, optical rotation, optical purity, and stereochemistry of the product were determined, and the results obtained are shown in Table 1. To the reaction mixture was added by heating up to room temperature The aqueous layer was removed the organic layer was washed successively with a 1:1 (by volume) mixture of aqueous ammonia a saturated ammonium chloride aqueous solution, a 5% hydrochloric acid aqueous solution, a saturated sodium chloride aqueous solution, and a saturated sodium carbonate aqueous solution, and dried over sodium sulfate The toluene was removed by distillation the residue was purified by silica gel column chromatography distilled under reduced pressure