2-azido-1-phenylethanone

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a stirred solution of α-azidoacetophenone (3.37 g, 20.9 mmol) in dry THF (50 mL) was added a solution of LDA (2.0 M in cyclohexane, 12.5 mL, 25 mmol) at -78° C. under nitrogen dropwise. After the reaction mixture was stirred for 1 h, a solution of 3-cyclopentylpropionyl chloride (5.04 g, 31.35 mmole, 1.5 eq.) was added to the dark red mixture, and after 10 min, the mixture was slowly warmed to room temperature. Stirring was continued for 1 h and the resultant yellow mixture was poured into water and extracted with ethyl acetate (3×50 mL). The combined organics were washed with water and brine, dried over magnesium sulfate, and filtered. Evaporation of solvent followed by column chromatography on silca gel (eluent: 2:1 ethyl acetate:hexanes) gave 4.0 g (71.5%) of the title compound: 1H NMR (400 MHz, CDCl3) ε 7.32-7.26 (m, 5H), 6.53 (s, 1H), 2.58 (t, 2H, J=7.5 Hz), 1.89-1.70 (m, 5H), 1,65-1.40 (m, 4H), 1.2 (m, 2H). after 10 min Stirring was continued for 1 h extracted with ethyl acetate (3×50 mL) The combined organics were washed with water and brine dried over magnesium sulfate filtered Evaporation of solvent

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

Procedure: To a stirred solution of α-azidoacetophenone (3.37 g, 20.9 mmol) in dry THF (50 mL) was added a solution of LDA (2.0 M in cyclohexane, 12.5 mL, 25 mmol) at -78° C. under nitrogen dropwise. After the reaction mixture was stirred for 1 h, a solution of 3-cyclopentylpropionyl chloride (5.04 g, 31.35 mmole, 1.5 eq.) was added to the dark red mixture, and after 10 min, the mixture was slowly warmed to room temperature. Stirring was continued for 1 h and the resultant yellow mixture was poured into water and extracted with ethyl acetate (3×50 mL). The combined organics were washed with water and brine, dried over magnesium sulfate, and filtered. Evaporation of solvent followed by column chromatography on silca gel (eluent: 2:1 ethyl acetate:hexanes) gave 4.0 g (71.5%) of the title compound: 1H NMR (400 MHz, CDCl3) ε 7.32-7.26 (m, 5H), 6.53 (s, 1H), 2.58 (t, 2H, J=7.5 Hz), 1.89-1.70 (m, 5H), 1,65-1.40 (m, 4H), 1.2 (m, 2H). after 10 min Stirring was continued for 1 h extracted with ethyl acetate (3×50 mL) The combined organics were washed with water and brine dried over magnesium sulfate filtered Evaporation of solvent

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 1-methyl-2-indolinethione (0.50 g, 3.06 mmol) in dry THF (3 mL) was added dropwise at 20° C. under N2 to a stirred suspension of NaH (0.13 g of a 60% w/w suspension in mineral oil, 3.37 mmol) in THF (2 mL). After gas evolution had ceased (5 minutes), a solution of the above phenacyl azide in THF (2 mL) was added dropwise, and the mixture was stirred at 20° C. for 1 hour, then poured into 6N HCl and extracted with EtOAc. The residue from the organic layer was chromatographed on silica gel. Elution with CH2Cl2 /petroleum ether (3:7) gave foreruns, and elution with CH2Cl2 /petroleum ether (2:3) gave 3-benzoyl-1-methyl-2-indolinethione [XV: R1 =H, R3 =Me, R5 =C6H5] (24) (0.31 g, 38%); mp (trituration from MeOH) 132°-134° C. (5 minutes) extracted with EtOAc The residue from the organic layer was chromatographed on silica gel Elution with CH2Cl2 /petroleum ether (3:7) gave foreruns, and elution with CH2Cl2 /petroleum ether (2:3)

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

Procedure: A solution of azide 2i (74 mg, 0.459 mmol) in anhydrous toluene (1.5 mL) was cooled to 0° C. A solution of phosphine 1e (171 mg, 0.482 mmol) in toluene (1.0 mL) was added dropwise. The resulting solution was maintained at 0° C. for 2 h and was then allowed to warm to room temperature. The mixture was then diluted with anhydrous CH2Cl2 (5 mL) and was stirred for an additional 30 min. The solution was then placed directly on a column of silica gel and eluted with 15% EtOAc/hexanes to give diazo-compound 5i as a yellow oil (33 mg, 0.226 mmol, 49% yield). to warm to room temperature eluted with 15% EtOAc/hexanes

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 1-methyl-2-indolinethione (0.50 g, 3.06 mmol) in dry THF (3 mL) was added dropwise at 20° C. under N2 to a stirred suspension of NaH (0.13 g of a 60% w/w suspension in mineral oil, 3.37 mmol) in THF (2 mL). After gas evolution had ceased (5 minutes), a solution of the above phenacyl azide in THF (2 mL) was added dropwise, and the mixture was stirred at 20° C. for 1 hour, then poured into 6N HCl and extracted with EtOAc. The residue from the organic layer was chromatographed on silica gel. Elution with CH2Cl2 /petroleum ether (3:7) gave foreruns, and elution with CHlCl2 /petroleum ether (2:3) gave 3-benzoyl-1-methyl-2-indolinethione [XV: R1 =H, R3 =Me, R5 =C6H5] (24) (0.31 g, 38%); mp (trituration from MeOH) 132°-134° C. (5 minutes) extracted with EtOAc The residue from the organic layer was chromatographed on silica gel Elution with CH2Cl2 /petroleum ether (3:7) gave foreruns, and elution with CHlCl2 /petroleum ether (2:3)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir: