Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1OB(O)O)=[O:2].Br[C:14]1[O:15][CH:16]=[CH:17][CH:18]=1.C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.CO>[O:15]1[CH:16]=[CH:17][CH:18]=[C:14]1[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[CH:1]=[O:2]
Reactant: Brc1ccco1
Reactant: O=Cc1ccccc1OB(O)O
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: Cc1ccccc1
Solvent: CO
Product: O=Cc1ccccc1-c1ccco1
Temperature: 80 °C
Reaction time: 6 h

Procedure:
2-Formylphenylboric acid (300 mg, 2.0 mmol), 2-bromofuran obtained in Example 64a (588 mg, 4.0 mmol), and tetrakis triphenylphosphine palladium (15 mg) were dissolved in a mixed solvent of toluene (38 ml) and methanol (5 ml). The solution was added with 2M aqueous sodium carbonate solution (20 ml) and heated at 80° C. with stirring for 6 hours. The reaction mixture was stand for cooling, and then the solvent was evaporated. The mixture was extracted with dichloromethane, and the extract was washed with a mixture of 2M aqueous sodium carbonate solution (10 ml) and aqueous solution of ammonia (2 ml), and dried over sodium sulfate. Insoluble solids were removed by filtration, and the filtrate was evaporated under reduced pressure to obtain the title compound as crude yellow oil (126 mg). The resulting crude product was used in the next reaction without purification.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[NH:8][C:7](=[O:14])[CH2:6]2.[N:15]1[CH:20]=[CH:19][C:18](/[CH:21]=[CH:22]/[C:23]2[C:31]3[C:26](=[CH:27][C:28]([CH:32]=O)=[CH:29][CH:30]=3)[NH:25][N:24]=2)=[CH:17][CH:16]=1>>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][C:11]=1[O:12][CH3:13])[NH:8][C:7](=[O:14])/[C:6]/2=[CH:32]/[C:28]1[CH:27]=[C:26]2[C:31]([C:23](/[CH:22]=[CH:21]/[C:18]3[CH:17]=[CH:16][N:15]=[CH:20][CH:19]=3)=[N:24][NH:25]2)=[CH:30][CH:29]=1
Reactant: O=Cc1ccc2c(/C=C/c3ccncc3)n[nH]c2c1
Reactant: COc1cc2c(cc1OC)NC(=O)C2
Product: COc1cc2c(cc1OC)/C(=C\c1ccc3c(/C=C/c4ccncc4)n[nH]c3c1)C(=O)N2
Yield: 42.4 %

Procedure:
The title compound (36 mg, 42%) was synthesized as an orange red solid according to the method described for Example A67 (oil temp 75° C., reflux 90 min) using 5,6-dimethoxyindolin-2-one (38.6 mg, 0.2 mmol) and (E)-3-(2-(pyridin-4-yl)vinyl)-1H-indazole-6-carbaldehyde (49.8 mg, 0.2 mmol). 1H NMR (400 MHz, DMSO-d6) δ 13.54 (s, 1H), 10.39 (s, 1H), 8.60-8.53 (m, 2H), 8.35 (d, J=7.2 Hz, 1H), 7.94 (s, 1H), 7.87 (d, J=16.4 Hz, 1H), 7.75-7.67 (m, 2H), 7.63-7.50 (m, 3H), 7.25 (s, 1H), 6.53 (s, 1H), 3.80 (s, 3H), 3.55 (s, 3H); MS ESI 425.2 [M+H]+, calcd for [C25H20N4O3+H]+ 425.1.
Reaction SMILES: [C:1]([Si:5]([CH3:21])([CH3:20])[O:6][CH2:7][CH2:8][S:9][C:10]1[N:15]=[C:14]([CH3:16])[C:13]([N+:17]([O-])=O)=[CH:12][CH:11]=1)([CH3:4])([CH3:3])[CH3:2].[NH4+].[Cl-]>C1COCC1.[Zn]>[C:1]([Si:5]([CH3:21])([CH3:20])[O:6][CH2:7][CH2:8][S:9][C:10]1[N:15]=[C:14]([CH3:16])[C:13]([NH2:17])=[CH:12][CH:11]=1)([CH3:4])([CH3:3])[CH3:2]
Reactant: Cc1nc(SCCO[Si](C)(C)C(C)(C)C)ccc1[N+](=O)[O-]
Agent: [Cl-]
Agent: [NH4+]
Agent: [Zn]
Solvent: C1CCOC1
Product: Cc1nc(SCCO[Si](C)(C)C(C)(C)C)ccc1N
Temperature: 25 °C
Reaction time: 3 h
Yield: 53.8 %

Procedure:
To a solution of 6-[2-(tert-butyl-dimethyl-silanyloxy)-ethylsulfanyl]-2-methyl-3-nitro-pyridine (80, 2.67 g, 8.1 mmol) in 15 mL THF, zinc dust (1.6 g, 24 mmol) followed by 8.2 mL (8.2 mmol) 1M NH4Cl solution was added. After stirring at room temperature for 3 h, more zinc dust (0.77 g, 8.13 mmol) and NH4Cl (0.43 g, 8.31 mmol) was added. After stirring for 4 h at mixture was filtered through celite and filtrate was extracted with CH2Cl2 and 1M NaOH. Organic phases were dried over MgSO4, filtered, and concentrated. Residue was purified by column chromatography (Hexane/AcOEt 3:1→2:1) to give 6-[2-(tert-butyl-dimethyl-silanyloxy)-ethylsulfanyl]-2-methyl-pyridin-3-ylamine as a yellowish oil (1.3 g, 54%). Exact mass calculated for C25H34BrN5O5 563.17. found 564.3 (MH+).
Reaction SMILES: [C:1]1([N:7]([CH2:30][C:31]([O:33][CH2:34][CH3:35])=[O:32])[C:8]([C:10]2[CH:29]=[CH:28][C:13]3[N:14]([CH3:27])[C:15]([CH2:17][CH2:18][C:19]4[CH:24]=[CH:23][C:22]([C:25]#[N:26])=[CH:21][CH:20]=4)=[N:16][C:12]=3[CH:11]=2)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[ClH:36].C(=O)([O-])[O-].[NH4+:41].[NH4+]>C(O)C>[ClH:36].[C:1]1([N:7]([CH2:30][C:31]([O:33][CH2:34][CH3:35])=[O:32])[C:8]([C:10]2[CH:29]=[CH:28][C:13]3[N:14]([CH3:27])[C:15]([CH2:17][CH2:18][C:19]4[CH:24]=[CH:23][C:22]([C:25](=[NH:41])[NH2:26])=[CH:21][CH:20]=4)=[N:16][C:12]=3[CH:11]=2)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: [NH4+]
Reactant: CCOC(=O)CN(C(=O)c1ccc2c(c1)nc(CCc1ccc(C#N)cc1)n2C)c1ccccc1
Agent: Cl
Agent: O=C([O-])[O-]
Solvent: CCO
Product: CCOC(=O)CN(C(=O)c1ccc2c(c1)nc(CCc1ccc(C(=N)N)cc1)n2C)c1ccccc1
Yield: 73 %

Procedure:
Prepared analogously to Example 25d from 1-methyl-2-[2-(4-cyanophenyl)ethyl]-benzimidazol-5-yl-carboxylic acid-N-phenyl-N-(ethoxycarbonylmethyl)-amide and ethanolic hydrochloric acid, ethanol and ammonium carbonate. Yield: 73% of theory, Rf value: 0.15 (silica gel; dichloromethane/ethanol=4:1) C28H29N5O3 (483.6) ##EQU19##
Reaction SMILES: [F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[NH:9][C:10]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)=[C:11]([C:19]([O:21]CC3C=CC=CC=3)=[O:20])[C:12]=2[C:13]2[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=2)=[CH:4][CH:3]=1>CCO.[Pd]>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[NH:9][C:10]([C:29]3[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=3)=[C:11]([C:19]([OH:21])=[O:20])[C:12]=2[C:13]2[CH:18]=[CH:17][N:16]=[CH:15][CH:14]=2)=[CH:6][CH:7]=1
Reactant: O=C(OCc1ccccc1)c1c(-c2ccccc2)[nH]c(-c2ccc(F)cc2)c1-c1ccncc1
Agent: [Pd]
Solvent: CCO
Product: O=C(O)c1c(-c2ccccc2)[nH]c(-c2ccc(F)cc2)c1-c1ccncc1

Procedure:
A mixture of benzyl 2-(4-fluorophenyl)-3-(4-pyridyl)-5-phenyl-pyrrole-4-carboxylate from Example 125 (1.0 mmol), 0.01 g of 10% Pd/C in 5 mL of EtOH will yield 2-(4-fluorophenyl)-3-(4-pyridyl)-5-phenyl-pyrrole-4-carboxylic acid after treatment with 40 psi H2 followed by filtration.
Reaction SMILES: [C:1]1([OH:14])[C:2]([C:7]2[C:8]([OH:13])=[CH:9][CH:10]=[CH:11][CH:12]=2)=[CH:3][CH:4]=[CH:5][CH:6]=1.[P:15](Cl)(Cl)[Cl:16]>>[P:15]1([Cl:16])[O:13][C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=2[O:14]1
Reactant: Oc1ccccc1-c1ccccc1O
Reactant: ClP(Cl)Cl
Product: Clp1oc2ccccc2c2ccccc2o1
Yield: 81 %

Procedure:
A solution of 2,2'-biphenol (28.1 g, 0.151 mol) in 49 mL phosphorus trichloride was heated at reflux for 2 hr. The excess PCl3 was removed by distillation. The residue was purified by vacuum distillation (140°-143° C. at 0.5 mm Hg) to give 30.70 g (81% yield) 1,1'-biphenyl-2,2'-diyl phosphorochloridite (as a clear viscous oil which solidified to a white solid upon standing at room temperature (RT) in an inert atmosphere for an extended period of time). 31P{1H}NMR (121.4 MHz, d8 -toluene): δ 180.1 (s), 85% H3PO4 external reference.
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][CH3:9])[C:3]=1[CH2:10][OH:11]>C(Cl)Cl.[O-2].[O-2].[Mn+4]>[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][CH3:9])[C:3]=1[CH:10]=[O:11]
Reactant: COc1cccc(N)c1CO
Agent: [Mn+4]
Agent: [O-2]
Solvent: ClCCl
Product: COc1cccc(N)c1C=O
Temperature: 25 °C
Reaction time: 24 h

Procedure:
A mixture of (2-Amino-6-methoxy-phenyl)-methanol (5.00 g, 0.033 mol) and manganese dioxide (13.7 g) in DCM (500 mL) iswas stirred at 25° C. for 24 h. The resulting solid is filtered off, washed with DCM to give the desired product.
Reaction SMILES: C(O)(C(F)(F)F)=O.[F:8][C:9]1[N:14]=[CH:13][C:12]([CH2:15][N:16]2[CH2:21][CH2:20][N:19](C(OC(C)(C)C)=O)[CH2:18][CH2:17]2)=[CH:11][C:10]=1[C:29]1[N:34]=[C:33]([CH3:35])[N:32]=[C:31]([S:36][CH3:37])[N:30]=1.C(Cl)Cl.C(N(CC)CC)C.[CH3:48][S:49](Cl)(=[O:51])=[O:50]>>[F:8][C:9]1[C:10]([C:29]2[N:34]=[C:33]([CH3:35])[N:32]=[C:31]([S:36][CH3:37])[N:30]=2)=[CH:11][C:12]([CH2:15][N:16]2[CH2:21][CH2:20][N:19]([S:49]([CH3:48])(=[O:51])=[O:50])[CH2:18][CH2:17]2)=[CH:13][N:14]=1
Reactant: CSc1nc(C)nc(-c2cc(CN3CCN(C(=O)OC(C)(C)C)CC3)cnc2F)n1
Reactant: CS(=O)(=O)Cl
Solvent: CCN(CC)CC
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: CSc1nc(C)nc(-c2cc(CN3CCN(S(C)(=O)=O)CC3)cnc2F)n1
Temperature: 25 °C
Reaction time: 1 h
Yield: 79 %

Procedure:
TFA (4.00 mL, 51.9 mmol) was slowly added to a stirred solution of tert-butyl 4-((6-fluoro-5-(4-methyl-6-(methylthio)-1,3,5-triazin-2-yl)pyridin-3-yl)methyl)piperazine-1-carboxylate (0.853 g, 1.963 mmol) in DCM (5.00 mL, 78 mmol) cooled in an ice bath, and the mixture was then stirred at room temperature for 1 h. The mixture was concentrated, and the sticky residue was dissolved in DCM (10 mL) and cooled in an ice bath, and triethylamine (1.368 mL, 9.82 mmol) was added. Methanesulfonyl chloride (0.459 mL, 5.89 mmol) was slowly added to the mixture, which was then stirred at the same temperature for 1 h, concentrated, and the residue was adsorbed onto a plug of silica gel and chromatographed through a RediSep®, Teledyne ISCO, Lincoln, Nebr., pre-packed silica gel column (pure DCM to 10% MeOH in DCM) to give a solid which was washed with IPA to give 2-(2-fluoro-5-((4-(methylsulfonyl)piperazin-1-yl)methyl)pyridin-3-yl)-4-methyl-6-(methylthio)-1,3,5-triazine (0.64 g, 79%) as a white solid. LCMS (API-ES) m/z 413 (M+H)+; 1H NMR (400 MHz, d6-DMSO) δ 8.58 (dd, J=9.29, 2.25 Hz, 1H) 8.37 (s, 1H) 3.67 (s, 2H) 3.01-3.19 (m, 4H) 2.87 (s, 3H) 2.61 (s, 3H) 2.60 (s, 3H) 2.47-2.49 (m, 4H).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[C:7]([OH:9])[CH:6]=[CH:5][C:4]=1[C:10]1[NH:11][C:12]2[C:13]([N:18]=1)=[N:14][CH:15]=[CH:16][CH:17]=2.[CH3:19][S:20](Cl)(=[O:22])=[O:21]>>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([O:9][S:20]([CH3:19])(=[O:22])=[O:21])[CH:6]=[CH:5][C:4]=1[C:10]1[NH:11][C:12]2[C:13]([N:18]=1)=[N:14][CH:15]=[CH:16][CH:17]=2
Reactant: COc1cc(O)ccc1-c1nc2ncccc2[nH]1
Reactant: CS(=O)(=O)Cl
Product: COc1cc(OS(C)(=O)=O)ccc1-c1nc2ncccc2[nH]1

Procedure:
Prepared analogously to Example 1 from 2-(2'-methoxy-4'-hydroxyphenyl)-imidazo[4,5-b]pyridine and methanesulfonic acid chloride.
Reaction SMILES: [NH:1]1[CH:5]=[CH:4][N:3]=[CH:2]1.Cl[C:7]1[N:8]=[C:9]([NH:18][CH2:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[C:22]([O:28][CH3:29])[CH:21]=2)[C:10]2[C:15]([CH3:16])=[C:14]([CH3:17])[S:13][C:11]=2[N:12]=1>>[N:1]1([C:7]2[N:8]=[C:9]([NH:18][CH2:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[C:22]([O:28][CH3:29])[CH:21]=3)[C:10]3[C:15]([CH3:16])=[C:14]([CH3:17])[S:13][C:11]=3[N:12]=2)[CH:5]=[CH:4][N:3]=[CH:2]1
Reactant: c1c[nH]cn1
Reactant: COc1ccc(CNc2nc(Cl)nc3sc(C)c(C)c23)cc1OC
Product: COc1ccc(CNc2nc(-n3ccnc3)nc3sc(C)c(C)c23)cc1OC

Procedure:
Following the procedure of Example 97, the reaction of imidazole with 2-chloro-5,6-dimethyl-4-(3,4-dimethoxybenzylamino)-thieno-[2,3-d]-pyrimidine gives 2-(imidazol-1-yl)-5,6-dimethyl-4-(3,4-dimethoxybenzylamino)-thieno-[2,3-d]-pyrimidine.
Reaction SMILES: [F:1][C:2]([F:34])([F:33])[C:3]1[CH:4]=[C:5]([CH:26]=[C:27]([C:29]([F:32])([F:31])[F:30])[CH:28]=1)[CH2:6][N:7]1[CH2:14][CH2:13][CH2:12][O:11][C:10]2[N:15]=[CH:16][CH:17]=[C:18]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:9]=2[C:8]1=[O:25].ClC1C=CC=C(C(OO)=[O:43])C=1>C(Cl)Cl>[F:34][C:2]([F:1])([F:33])[C:3]1[CH:4]=[C:5]([CH:26]=[C:27]([C:29]([F:32])([F:31])[F:30])[CH:28]=1)[CH2:6][N:7]1[CH2:14][CH2:13][CH2:12][O:11][C:10]2[N+:15]([O-:43])=[CH:16][CH:17]=[C:18]([C:19]3[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=3)[C:9]=2[C:8]1=[O:25]
Reactant: O=C1c2c(-c3ccccc3)ccnc2OCCCN1Cc1cc(C(F)(F)F)cc(C(F)(F)F)c1
Reactant: O=C(OO)c1cccc(Cl)c1
Solvent: ClCCl
Product: O=C1c2c(-c3ccccc3)cc[n+]([O-])c2OCCCN1Cc1cc(C(F)(F)F)cc(C(F)(F)F)c1
Temperature: 25 °C
Reaction time: 24 h
Yield: 54.6 %

Procedure:
5-[3,5-bis(trifluoromethyl)benzyl]-6-oxo-7-phenyl-2,3,4,5-tetrahydro-6H-pyrido[2,3-b][1,5]oxazocine (729 mg) was dissolved in methylene chloride (10 mL) and 3-chloroperbenzoic acid (524 mg) was added to the solution. The resulting mixture was then stirred at room temperature for 24 hours. The reaction mixture was purified on a silica gel column chromatography (ethyl acetate:methanol=5:1) to obtain 5-[3,5-bis(trifluoromethyl)benzyl]-6-oxo-7-phenyl-2,3,4,5-tetrahydro-6H-pyrido[2,3-b][1,5]oxazocine 10-oxide (411 mg, 54%).