Reaction SMILES: [CH3:1][O:2][C:3]([C:5]1[S:12][C:11]2[CH:10]=[N:9][N:8](C(=O)C)[C:7]=2[CH:6]=1)=[O:4].C[O-].[Na+].[I:19]I>CO.CN(C)C=O>[CH3:1][O:2][C:3]([C:5]1[S:12][C:11]2[C:10]([I:19])=[N:9][NH:8][C:7]=2[CH:6]=1)=[O:4]
Reactant: II
Reactant: COC(=O)c1cc2c(cnn2C(C)=O)s1
Agent: C[O-]
Agent: [Na+]
Solvent: CN(C)C=O
Solvent: CO
Product: COC(=O)c1cc2[nH]nc(I)c2s1
Temperature: 60 °C
Reaction time: 0.33 h
Yield: 88.6 %

Procedure:
5-Methyl-4-nitro-thiophene-2-carboxylic acid is prepared according to Snider et al. (H. R. Snider and L. A. Carpino, J. F. Zack, Jr., J. F. Mills, J. Am. Chem. Soc., 1951, 79, 2556-2559) from commercially available 5-methylthiophene-2-carboxylic acid and is esterified according to known processes (P. Cogolli, F. Maiolo, L. Testaferri, M. Tiecco, M. Tingoli, J. Chem. Soc., Perkin I, 1980, 1331-1335; V. M. Colburn, B. Iddon, H. Shuschitzky, J. Chem. Soc., Perkin I, 1977, 2436-2441) to obtain 5-methyl-4-nitro-thiophene-2-carboxylic acid methyl ester [Intermediate (23)]. Step 2. 5-Methyl-4-nitro-thiophene-2-carboxylic acid methyl ester [15.09 g., 75.0 mM, Intermediate (23)] is dissolved in ethyl acetate (200 mL) to which 10% palladium on charcoal (1.03 g) is added and the mixture is shaken under 50 psi of hydrogen. The catalyst is removed by filtration and the solvent is removed leaving 4-amino-5-methyl-thiophene-2-carboxylic acid methyl ester [12.82 g., 99.8%, Intermediate (24)] as a yellow solid; MS 171.9 (100%, M+1). Step 3. A magnetically stirred mixture of potassium acetate (4.52 g, 46.1 mM) in toluene (100 mL) containing 4-amino-5-methyl-thiophene-2-carboxylic acid methyl ester [12.8 g, 74.7 mM, Intermediate (24)] is warmed to dissolve the amine. Acetic anhydride (13.8 mL, 124.9 mM) is added to this mixture and it is heated in an oil bath. Isoamyl nitrite (9.73 mL, 72.4 mM) is added over 30 minutes. Heating at 93° C. is continued overnight. The cooled mixture is diluted with ethyl acetate (100 mL), filtered and the filtrate is concentrated to a black solid which is purified by chromatography, eluting with heptane-25% ethyl acetate, heptane-35% ethyl acetate, heptane-40% ethyl acetate, heptane-50% ethyl acetate, heptane-60% ethyl acetate. Fractions containing pure product are combined and concentrated to afford 1-acetyl-1 H-thieno[3,2-c]pyrazole-5-carboxylic acid methyl ester [9.74 g, 49.3%, Intermediate (25)]. Step 4. To a suspension of 1-acetyl-1H-thieno[3,2-c]pyrazole-5-carboxylic acid methyl ester [1.3 g, 5.79 mmol, Intermediate (25)] in methanol (30 mL) is added sodium methoxide (25 wt % in methanol). The resulting solution mixture is stirred at 60° C. oil bath for 20 minutes. The oil bath is removed and stirred for 5 minutes. To this is added a solution of iodine (1.76 g, 6.93 mmol) in dimethyl formamide (2 mL). The reaction mixture then heated to 60° C. for 1 hour. The solvent is removed in vacuo. The crude is partitioned between ethyl acetate (100 mL) and water (100 mL) and aqueous layer is further extracted with twice ethyl acetate (25 mL). The combined ethyl acetate phases are washed with brine, dried over sodium sulfate and filtered. The solvent is removed in vacuo to give 3-iodo-1H-thieno[3,2-c]pyrazole-5-carboxylic acid methyl ester [1.58 g, 89%, Intermediate (26)] as light yellow solid; 1H NMR [(CD3)2SO)]: δ 13.80 (1H, brs, NH), 7.947 (1H, s), 3.870 (3H, s). Step 5. To a mixture of 3-iodo-1H-thieno[3,2-c]pyrazole-5-carboxylic acid methyl ester [1.5 g, 4.87 mmol, Intermediate (26)] in tetrahydrofuran (120 mL) is added 4(dimethylamino)pyridine (8 mg) and di-tert-butyl-dicarbonate (1M in tetrahydrofuran, 5.3 mL) dropwise at room temperature. After stirring for 30 minutes, the solvent is removed in vacuo. The solid is suspended in a mixture of ethyl acetate, heptane and methanol and stirred for a while. The solid is filtered and vacuum dried to give 3-iodo-thieno[3,2-c]pyrazole-1,5-dicarboxylic acid 1-tert-butyl ester 5-methyl ester [1.72 g, 87%, Intermediate (21)] as off-white solid; 1H NMR [(CD3)2SO)]: δ 6.880 (1H, s), 3.900 (3H, s), 1.633 (9H, s); LC/MS: 409 (M+H).