ethyl 3-oxo-1,2-dihydroindene-2-carboxylate

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Carbethoxy-1-indanone was dissolved in dry methanol at room temperature, to which sodium borohydride was added in three lots while the reaction mixture was kept stirring. The reaction mixture was further stirred for 30 minutes, after which the solid was filtered and the filtrate was evaporated to dryness. The residue was dissolved in dry benzene, to which catalytic amount of p-toluenesulfonic acid was added and the reaction mixture was stirred for one hour. The p-toluenesulfonic acid was filtered off and the filtrate was concentrated to yield ethyl indene-2-carboxylate. The ethyl indene-2-carboxylate was dissolved in methanol and 1.0 equivalent of aqueous sodium hydroxide solution was added and the reaction mixture was kept stirring for overnight. The next day, the reaction was terminated by evaporating the methanol, followed by diluting the residue with water, brought to neutral pH and the precipitated indene-2-carboxylic acid was filtered. NMR: (CDCl3):δ:3.75 (s, 2H, benzylic CH2); 7.4-7.7 (m, 4H, Ar-H); 7.95 (s, 1H, olefinic H). was added in three lots while the reaction mixture The reaction mixture was further stirred for 30 minutes after which the solid was filtered the filtrate was evaporated to dryness The residue was dissolved in dry benzene, to which catalytic amount of p-toluenesulfonic acid was added the reaction mixture was stirred for one hour The p-toluenesulfonic acid was filtered off the filtrate was concentrated

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Indanone (1.5 g, 11.36 mmols) was dissolved in dry THF in a three neck flask equipped with nitrogen inlet, septum and a guard tube. The flask was cooled to -20° C. for 10 minutes. Then butyl lithium (11.37 ml, 12.48 mmols) was added dropwise through the septum using the syringe. The reaction mixture was allowed to stand at -20° C. for 45 minutes and then ethyl chloroformate (1.08 ml, 10 mmols) was added dropwise using a syringe. The reaction mixture was stirred at -20° C. for 30 minutes and slowly brought to room temperature in about one hour. The reaction was worked-up by evaporating the THF and the product was chromatographed to yield 2-carbethoxy-1-indanone. NMR: (CDCl3):δ:1.25 (t, 3H, OCH2CH3); 3.45 (d, 2H, benzylic CH2); 3.65 (t, 1H, COCHCO); 4.2 (q, 2H, OCH2CH3); 7.4-7.5 (m, 4H, Ar-H). equipped with nitrogen inlet slowly brought to room temperature in about one hour by evaporating the THF the product was chromatographed

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Carbethoxy-1-indanone was dissolved in dry methanol at room temperature, to which sodium borohydride was added in three lots while the reaction mixture was kept stirring. The reaction mixture was further stirred for 30 minutes, after which the solid was filtered and the filtrate was evaporated to dryness. The residue was dissolved in dry benzene, to which catalytic amount of p-toluenesulfonic acid was added and the reaction mixture was stirred for one hour. The p-toluenesulfonic acid was filtered off and the filtrate was concentrated to yield ethyl indene-2-carboxylate. The ethyl indene-2-carboxylate was dissolved in methanol and 1.0 equivalent of aqueous sodium hydroxide solution was added and the reaction mixture was kept stirring for overnight. The next day, the reaction was terminated by evaporating the methanol, followed by diluting the residue with water, brought to neutral pH and the precipitated indene-2-carboxylic acid was filtered. NMR: (CDCl3):δ:3.75 (s, 2H, benzylic CH2); 7.4-7.7 (m, 4H, Ar-H); 7.95 (s, 1H, olefinic H). was added in three lots while the reaction mixture The reaction mixture was further stirred for 30 minutes after which the solid was filtered the filtrate was evaporated to dryness The residue was dissolved in dry benzene, to which catalytic amount of p-toluenesulfonic acid was added the reaction mixture was stirred for one hour The p-toluenesulfonic acid was filtered off the filtrate was concentrated

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Indanone (1.5 g, 11.36 mmols) was dissolved in dry THF in a three neck flask equipped with nitrogen inlet, septum and a guard tube. The flask was cooled to -20° C. for 10 minutes. Then butyl lithium (11.37 ml, 12.48 mmols) was added dropwise through the septum using the syringe. The reaction mixture was allowed to stand at -20° C. for 45 minutes and then ethyl chloroformate (1.08 ml, 10 mmols) was added dropwise using a syringe. The reaction mixture was stirred at -20° C. for 30 minutes and slowly brought to room temperature in about one hour. The reaction was worked-up by evaporating the THF and the product was chromatographed to yield 2-carbethoxy-1-indanone. NMR: (CDCl3):δ:1.25 (t, 3H, OCH2CH3); 3.45 (d, 2H, benzylic CH2); 3.65 (t, 1H, COCHCO); 4.2 (q, 2H, OCH2CH3); 7.4-7.5 (m, 4H, Ar-H). equipped with nitrogen inlet slowly brought to room temperature in about one hour by evaporating the THF the product was chromatographed

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Colletotrichum gloeosporioides is cultured according to the method of Buisson and Azerad (Tet. Lett. 27, 2631-2634 (1986), herein incorporated by reference) in one liter of a medium of glucose (30 grams), KH2PO4 (1 gram), K2HPO4 (2 grams), corn steep liquor (10 grams) MgSO4.7H2O (0.5 gram), NaNO3 (2 grams), FeSO4.7H2O (0.02 gram), and KCl (0.5 gram) with rotary shaking at 25° C. Two grams of 2-carboethoxy-1-indanone is dissolved in 2 ml of 95% ethanol the resulting solution is added to the culture, and shaking is resumed. The reaction is followed by TLC (staining with anisaldehyde) to monitor the consumption of starting material and the production of product alcohol. After approximately 48 hours the reaction is judged complete, and the reaction is terminated by removing from the shaker and adding 20-30 grams of Celite. The resulting suspension is suction filtered through a pad of Celite and the clear yellow filtrate is extracted with ethyl acetate (4×200 ml). The extracts are combined, dried over MgSO4, filtered, and rotary evaporated to leave 1.7 grams of (1S,2S)-1-hydroxy-2-carboethoxyindane as a yellow oil. The chiral purity of the product is greater than 98% as judged by chiral chromatography. is added to the culture the consumption of starting material the reaction is terminated by removing from the shaker adding 20-30 grams of Celite filtered through a pad of Celite the clear yellow filtrate is extracted with ethyl acetate (4×200 ml) dried over MgSO4 filtered rotary evaporated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Carbethoxy-1-indanone was dissolved in dry methanol at room temperature, to which sodium borohydride was added in three lots while the reaction mixture was kept stirring. The reaction mixture was further stirred for 30 minutes, after which the solid was filtered and the filtrate was evaporated to dryness. The residue was dissolved in dry benzene, to which catalytic amount of p-toluenesulfonic acid was added and the reaction mixture was stirred for one hour. The p-toluenesulfonic acid was filtered off and the filtrate was concentrated to yield ethyl indene-2-carboxylate. The ethyl indene-2-carboxylate was dissolved in methanol and 1.0 equivalent of aqueous sodium hydroxide solution was added and the reaction mixture was kept stirring for overnight. The next day, the reaction was terminated by evaporating the methanol, followed by diluting the residue with water, brought to neutral pH and the precipitated indene-2-carboxylic acid was filtered. NMR: (CDCl3):δ:3.75 (s, 2H, benzylic CH2); 7.4-7.7 (m, 4H, Ar-H); 7.95 (s, 1H, olefinic H). was added in three lots while the reaction mixture The reaction mixture was further stirred for 30 minutes after which the solid was filtered the filtrate was evaporated to dryness The residue was dissolved in dry benzene, to which catalytic amount of p-toluenesulfonic acid was added the reaction mixture was stirred for one hour The p-toluenesulfonic acid was filtered off the filtrate was concentrated

反応条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-Indanone (1.5 g, 11.36 mmols) was dissolved in dry THF in a three neck flask equipped with nitrogen inlet, septum and a guard tube. The flask was cooled to -20° C. for 10 minutes. Then butyl lithium (11.37 ml, 12.48 mmols) was added dropwise through the septum using the syringe. The reaction mixture was allowed to stand at -20° C. for 45 minutes and then ethyl chloroformate (1.08 ml, 10 mmols) was added dropwise using a syringe. The reaction mixture was stirred at -20° C. for 30 minutes and slowly brought to room temperature in about one hour. The reaction was worked-up by evaporating the THF and the product was chromatographed to yield 2-carbethoxy-1-indanone. NMR: (CDCl3):δ:1.25 (t, 3H, OCH2CH3); 3.45 (d, 2H, benzylic CH2); 3.65 (t, 1H, COCHCO); 4.2 (q, 2H, OCH2CH3); 7.4-7.5 (m, 4H, Ar-H). equipped with nitrogen inlet slowly brought to room temperature in about one hour by evaporating the THF the product was chromatographed