methyl 2-iodobenzoate

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:

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:

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 2-iodo-benzoic acid methyl ester (792 mg, 3.02 mmol) in DMF (10 mL) are added trimethylsilylacetylene (854 μL, 6.04 mmol) and triethylamine (2.95 mL, 21.1 mmol). The reaction mixture is degassed for 20 minutes with a stream of nitrogen. Dichloro(bistriphenylphosphene) palladium (II) (212 mg, 0.302 mmol, 10 mol %) and copper (I) iodide (58 mg, 0.302 mmol, 10 mol %) are added and the reaction is heated to 80° C. After 3 h, the reaction is concentrated and the residue is chromatographed eluting with 0 to 5% EtOAc/Hexanes to yield the title compound (597 mg, 85%). GC/MS: 232. The reaction mixture is degassed for 20 minutes with a stream of nitrogen the reaction is concentrated the residue is chromatographed eluting with 0 to 5% EtOAc/Hexanes

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

Procedure: Step 1--A mixture of methyl o-iodobenzoate (9.17 g), propargyl alcohol (3.06 ml) and diethyl amine (90 ml) is treated with bis(triphenylphosphine)palladium chloride (1.23 g) and copper iodide (333 mg) and the reaction is stirred at 20-25° under nitrogen for 18 hrs. The reaction is then filtered through a filter agent and concentrated. The resulting residue is partitioned between water and dichloromethane. The combined organic phases are washed once with saline, dried over magnesium sulfate, filtered and concentrated to an oil. Purification by silica gel chromatography gives methyl o-(1-hydroxy-2-propyn-3-yl)benzoate (CXIX). The reaction is then filtered through a filter agent concentrated The resulting residue is partitioned between water and dichloromethane The combined organic phases are washed once with saline dried over magnesium sulfate filtered concentrated to an oil Purification by silica gel chromatography