6-氧代己酸乙酯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask containing ethyl 6-hydroxyhexanoate (4.07 mL, 25.0 mmol) in CH2Cl2 (25 mL) was added TEMPO (391 mg, 2.50 mmol) followed by iodobenzene diacetate (8.86 g, 27.5 mmol). The reaction was stirred 2 hours and then diluted with CH2Cl2 (100 mL). Saturated aqueous solution of Na2S2O3 (100 mL) was added and extracted with CH2Cl2 (3×50 mL). The combined organics were washed with saturated aqueous NaHCO3 (150 mL) and brine (150 mL), dried over Na2SO4, and concentrated in vacuo. The resulting residue was purified by silica gel chromatography (20-40% Et2O/pentanes) to provide the title compound, which was identical to the reported literature compound. (See: Taber, D. F.; Teng, D. (2002) J. Org. Chem., 67: 1607.) extracted with CH2Cl2 (3×50 mL) The combined organics were washed with saturated aqueous NaHCO3 (150 mL) and brine (150 mL) dried over Na2SO4 concentrated in vacuo The resulting residue was purified by silica gel chromatography (20-40% Et2O/pentanes)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A yellow solution of ethyl 6-oxohexanoate (44.80 mmol) in DCM (92 ml) was treated with 2-methylpropane-2-sulfinamide (5.431 g; 44.80 mmol) and with anh. CuSO4 (14.302 g; 89.61 mmol). The resulting beige heterogeneous mixture was further stirred at rt, under nitrogen, for 24 h. The resulting heterogeneous mixture was then filtered over a short pad of celite, and the separated solids were further washed with DCM. The obtained orange filtrate was concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=25/1) afforded ethyl 6-((tert-butylsulfinyl)imino)hexanoate as a yellow/orange oil. LC-MS (conditions B): tR=0.81 min.; [M+H]+: 262.07 g/mol. The resulting heterogeneous mixture was then filtered over a short pad of celite the separated solids were further washed with DCM The obtained orange filtrate was concentrated to dryness under reduced pressure Purification by FC (DCM/MeOH=25/1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A colorless solution of commercially available ethyl hept-6-enoate (7.000 g; 44.80 mmol) in dioxane (330 ml) and water (110 ml) was treated successively with 2,6-lutidine (9.603 g; 89.61 mmol), a solution of osmium tetroxide (2.5 wt. % in 2-methylpropan-2-ol; 0.56 ml), and NaIO4 (38.335 g; 179.23 mmol). The resulting beige heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 13.5 h. The resulting milky mixture was treated with water (100 ml) and DCM (500 ml). The layers were separated, and the aq. layer was further extracted with DCM (200 ml/150 ml). The mixed slightly yellow organic layers were then washed with brine (200 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure to give crude ethyl 6-oxohexanoate as a dark-yellow/brown oil which was directly used for the next step without additional purification. The resulting beige heterogeneous reaction mixture The layers were separated the aq. layer was further extracted with DCM (200 ml/150 ml) The mixed slightly yellow organic layers were then washed with brine (200 ml) dried over anh. MgSO4 filtered concentrated to dryness under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A colorless solution of commercially available ethyl hept-6-enoate (7.000 g; 44.80 mmol) in dioxane (330 ml) and water (110 ml) was treated successively with 2,6-lutidine (9.603 g; 89.61 mmol), a solution of osmium tetroxide (2.5 wt. % in 2-methylpropan-2-ol; 0.56 ml), and NaIO4 (38.335 g; 179.23 mmol). The resulting beige heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 13.5 h. The resulting milky mixture was treated with water (100 ml) and DCM (500 ml). The layers were separated, and the aq. layer was further extracted with DCM (200 ml/150 ml). The mixed slightly yellow organic layers were then washed with brine (200 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure to give crude ethyl 6-oxohexanoate as a dark-yellow/brown oil which was directly used for the next step without additional purification. The resulting beige heterogeneous reaction mixture The layers were separated the aq. layer was further extracted with DCM (200 ml/150 ml) The mixed slightly yellow organic layers were then washed with brine (200 ml) dried over anh. MgSO4 filtered concentrated to dryness under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 2,3-di-p-tolyl-5,6,7,8-tetrahydropyrido[2,3-b]pyrazine (Intermediate B) (2.0 g, 6.34 mmol) and ethyl 6-oxohexanoate (Intermediate A) (2.508 g, 12.68 mmol) in 1,2-dichloroethane (50 ml) was treated with sodium triacetoxyborohydride (3.36 g, 15.85 mmol) and the resultant suspension was stirred at room temperature overnight. The solution was treated with sat.NaHCO3 and extracted with DCM (×3). The organic extracts were dried (MgSO4) and evaporated under reduced pressure. The residue was loaded onto an Isolute® SCX-2 cartridge and eluted with MeOH followed by 2M NH3 in MeOH. The methanolic ammonia fractions were concentrated under reduced pressure and further purified by chromatography on silica eluting with 10-50% EtOAc in iso-hexane to afford the titled compound; The solution was treated NaHCO3 and extracted with DCM (×3) The organic extracts were dried (MgSO4) evaporated under reduced pressure eluted with MeOH The methanolic ammonia fractions were concentrated under reduced pressure further purified by chromatography on silica eluting with 10-50% EtOAc in iso-hexane

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 2,3-di-p-tolyl-5,6,7,8-tetrahydropyrido[2,3-b]pyrazine (Intermediate B) (2.0 g, 6.34 mmol) and ethyl 6-oxohexanoate (Intermediate A) (2.508 g, 12.68 mmol) in 1,2-dichloroethane (50 ml) was treated with sodium triacetoxyborohydride (3.36 g, 15.85 mmol) and the resultant suspension was stirred at room temperature overnight. The solution was treated with sat.NaHCO3 and extracted with DCM (×3). The organic extracts were dried (MgSO4) and evaporated under reduced pressure. The residue was loaded onto an Isolute® SCX-2 cartridge and eluted with MeOH followed by 2M NH3 in MeOH. The methanolic ammonia fractions were concentrated under reduced pressure and further purified by chromatography on silica eluting with 10-50% EtOAc in iso-hexane to afford the titled compound; The solution was treated NaHCO3 and extracted with DCM (×3) The organic extracts were dried (MgSO4) evaporated under reduced pressure eluted with MeOH The methanolic ammonia fractions were concentrated under reduced pressure further purified by chromatography on silica eluting with 10-50% EtOAc in iso-hexane

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of pyridinium chlorochromate (2.0 g) in dichloromethane (15 ml) was added a solution of 6-hydroxyhexanoic acid ethyl ester (1.0 g) in dichloromethane (1.5 ml) in one portion and stirred for 1.5 hours at ambient temperature. Ether (15 ml) was added to the reaction mixture, and the insoluble material removed by filtration and discarded. The filtrate was purified by silica gel chromatography (diethyl ether) to give 6-oxohexanoic acid ethyl ester (884.6 mg), as a pale green oil. the insoluble material removed by filtration The filtrate was purified by silica gel chromatography (diethyl ether)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a flask containing ethyl 6-hydroxyhexanoate (4.07 mL, 25.0 mmol) in CH2Cl2 (25 mL) was added TEMPO (391 mg, 2.50 mmol) followed by iodobenzene diacetate (8.86 g, 27.5 mmol). The reaction was stirred 2 hours and then diluted with CH2Cl2 (100 mL). Saturated aqueous solution of Na2S2O3 (100 mL) was added and extracted with CH2Cl2 (3×50 mL). The combined organics were washed with saturated aqueous NaHCO3 (150 mL) and brine (150 mL), dried over Na2SO4, and concentrated in vacuo. The resulting residue was purified by silica gel chromatography (20-40% Et2O/pentanes) to provide the title compound, which was identical to the reported literature compound. (See: Taber, D. F.; Teng, D. (2002) J. Org. Chem., 67: 1607.) extracted with CH2Cl2 (3×50 mL) The combined organics were washed with saturated aqueous NaHCO3 (150 mL) and brine (150 mL) dried over Na2SO4 concentrated in vacuo The resulting residue was purified by silica gel chromatography (20-40% Et2O/pentanes)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A yellow solution of ethyl 6-oxohexanoate (44.80 mmol) in DCM (92 ml) was treated with 2-methylpropane-2-sulfinamide (5.431 g; 44.80 mmol) and with anh. CuSO4 (14.302 g; 89.61 mmol). The resulting beige heterogeneous mixture was further stirred at rt, under nitrogen, for 24 h. The resulting heterogeneous mixture was then filtered over a short pad of celite, and the separated solids were further washed with DCM. The obtained orange filtrate was concentrated to dryness under reduced pressure. Purification by FC (DCM/MeOH=25/1) afforded ethyl 6-((tert-butylsulfinyl)imino)hexanoate as a yellow/orange oil. LC-MS (conditions B): tR=0.81 min.; [M+H]+: 262.07 g/mol. The resulting heterogeneous mixture was then filtered over a short pad of celite the separated solids were further washed with DCM The obtained orange filtrate was concentrated to dryness under reduced pressure Purification by FC (DCM/MeOH=25/1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A colorless solution of commercially available ethyl hept-6-enoate (7.000 g; 44.80 mmol) in dioxane (330 ml) and water (110 ml) was treated successively with 2,6-lutidine (9.603 g; 89.61 mmol), a solution of osmium tetroxide (2.5 wt. % in 2-methylpropan-2-ol; 0.56 ml), and NaIO4 (38.335 g; 179.23 mmol). The resulting beige heterogeneous reaction mixture was further stirred at rt, under nitrogen, for 13.5 h. The resulting milky mixture was treated with water (100 ml) and DCM (500 ml). The layers were separated, and the aq. layer was further extracted with DCM (200 ml/150 ml). The mixed slightly yellow organic layers were then washed with brine (200 ml), dried over anh. MgSO4, filtered, and concentrated to dryness under reduced pressure to give crude ethyl 6-oxohexanoate as a dark-yellow/brown oil which was directly used for the next step without additional purification. The resulting beige heterogeneous reaction mixture The layers were separated the aq. layer was further extracted with DCM (200 ml/150 ml) The mixed slightly yellow organic layers were then washed with brine (200 ml) dried over anh. MgSO4 filtered concentrated to dryness under reduced pressure