Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:12][C:11]3[CH:13]=[C:14]([OH:17])[CH:15]=[CH:16][C:10]=3[C:9]=2[C:18]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][N:29]3[CH2:34][CH2:33][CH2:32][CH2:31][CH2:30]3)=[CH:22][CH:21]=2)=[O:19])=[CH:4][CH:3]=1.CN(C1C=CC=CN=1)C.[Si:44](Cl)([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45]>C1COCC1.CN(C=O)C>[Si:44]([O:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[S:12][C:11]3[CH:13]=[C:14]([OH:17])[CH:15]=[CH:16][C:10]=3[C:9]=2[C:18]([C:20]2[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][N:29]3[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34]3)=[CH:22][CH:21]=2)=[O:19])=[CH:4][CH:3]=1)([C:47]([CH3:50])([CH3:49])[CH3:48])([CH3:46])[CH3:45]
Reactant: CC(C)(C)[Si](C)(C)Cl
Reactant: O=C(c1ccc(OCCN2CCCCC2)cc1)c1c(-c2ccc(O)cc2)sc2cc(O)ccc12
Agent: CN(C)c1ccccn1
Solvent: CN(C)C=O
Solvent: C1CCOC1
Product: CC(C)(C)[Si](C)(C)Oc1ccc(-c2sc3cc(O)ccc3c2C(=O)c2ccc(OCCN3CCCCC3)cc2)cc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 45 %

Procedure:
A solution was prepared consisting of 10 g (21.1 mmol) of [2-(4-hydroxyphenyl)-6-hydroxybenzo[b]thien-3-yl][4-[2-(1-piperidinyl)ethoxy]phenyl]methanone and 6 g (49.1 mmol) of dimethylaminopyridine in 700 mL of THF-DMF (6:1)(v/v). This solution was stirred for one hour at ambient temperature and then cooled to 0° C. in an ice bath. To this solution was added 2.9 g (19.3 mmol) of tert-butyl-dimethylsilylchloride. The reaction mixture was stirred under a nitrogen atmosphere and allowed to warm to ambient temperature. After seventy-two hours, the reaction was quenched with the addition of a saturated solution of aqueous NH4Cl. The organic layer was separated and washed with water, brine, and finally dried by filtration through anhydrous Na2SO4 and evaporated to dryness The crude product was triturated with CH2Cl2, allowed to stand for three hours, and filtered to remove unreacted starting material. This resulting product is a mixture of isomers, which are separated by chromatography on a silica gel column eluted with a linear gradient beginning with CHCl3 and ending with CHCl3 --MeOH (19:1)(v/v). The desired fractions were determined by tlc, combined, and evaporated to dryness. This yielded 5.1 g of the title compound, isolated as a yellow crystalline solid.
Reaction SMILES: Br[C:2]1[C:7]2[NH:8][C:9]([N:11]3[CH2:16][CH2:15][N:14]([C:17]4[N:22]=[CH:21][C:20]([CH2:23][OH:24])=[CH:19][C:18]=4[Cl:25])[CH2:13][CH2:12]3)=[N:10][C:6]=2[CH:5]=[C:4]([C:26]([F:29])([F:28])[F:27])[CH:3]=1.[F:30][C:31]1[CH:32]=[C:33](B(O)O)[CH:34]=[CH:35][C:36]=1[O:37][CH3:38]>>[Cl:25][C:18]1[CH:19]=[C:20]([CH2:23][OH:24])[CH:21]=[N:22][C:17]=1[N:14]1[CH2:13][CH2:12][N:11]([C:9]2[NH:8][C:7]3[C:2]([C:33]4[CH:34]=[CH:35][C:36]([O:37][CH3:38])=[C:31]([F:30])[CH:32]=4)=[CH:3][C:4]([C:26]([F:29])([F:27])[F:28])=[CH:5][C:6]=3[N:10]=2)[CH2:16][CH2:15]1
Reactant: COc1ccc(B(O)O)cc1F
Reactant: OCc1cnc(N2CCN(c3nc4cc(C(F)(F)F)cc(Br)c4[nH]3)CC2)c(Cl)c1
Product: COc1ccc(-c2cc(C(F)(F)F)cc3nc(N4CCN(c5ncc(CO)cc5Cl)CC4)[nH]c23)cc1F

Procedure:
(6-{4-[7-Bromo-5-(trifluoromethyl)-1H-benzimidazol-2-yl]piperazin-1-yl}-5-chloropyridin-3-yl)methanol from step (a) above (98 mg, 0.2 mmol) and 3-fluoro-4-methoxyphenylboronic acid (43 mg, 0.25 mmol, Aldrich) reacted under the conditions of Example 51 to give the title compound as a white amorphous solid. MS (ESI, pos. ion) m/z: 536 (M+1).
Reaction SMILES: [Br:1][C:2]1[C:3]([F:12])=[CH:4][C:5]([N+:9]([O-])=O)=[C:6]([OH:8])[CH:7]=1.O.O.[Sn](Cl)Cl.C[CH2:19][OH:20].C(N1C=CN=C1)(N1C=CN=C1)=O>C1COCC1>[Br:1][C:2]1[C:3]([F:12])=[CH:4][C:5]2[NH:9][C:19](=[O:20])[O:8][C:6]=2[CH:7]=1
Reactant: O=[N+]([O-])c1cc(F)c(Br)cc1O
Reactant: CCO
Agent: Cl[Sn]Cl
Agent: O=C(n1ccnc1)n1ccnc1
Solvent: C1CCOC1
Solvent: O
Product: O=c1[nH]c2cc(F)c(Br)cc2o1
Temperature: 70 °C
Yield: 71.6 %

Procedure:
To a 100 mL of round bottom flask was added 5-bromo-4-fluoro-2-nitrophenol (0.98 g, 4.15 mmol), tin(II) chloride dihydrate (4.73 g, 20.76 mmol) and 5 mL of EtOH. The reaction mixture was heated to 70° C. for 30 minutes. The reaction mixture was concentrated and washed with saturated NaHCO3 solution, and extracted with DCM (100 mL×3), and concentrated providing the crude product. 1,1′-Carbonyldiimidazole (808 mg, 4983 mmol) was added to the crude product in 20 mL of THF. The reaction mixture was heated at reflux overnight. The reaction mixture was concentrated and purified with silica gel column chromatography, eluting with 0-30% EtOAc/hexane to give 6-bromo-5-fluorobenzo[d]oxazol-2(3H)-one (690 mg, 71.6% yield). MS m/z: 232 (M+1).
Reaction SMILES: C(O[CH:5]1[O:34][C@H:33]([CH2:35][O:36][CH2:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C@H:24]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@H:6]1[O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)(=O)C.[BrH:44].C(=O)([O-])O.[Na+]>C1(C)C=CC=CC=1.C(OC(C)C)(C)C>[CH2:8]([O:7][C@@H:6]1[C@@H:15]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@@H:24]([O:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[C@@H:33]([CH2:35][O:36][CH2:37][C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[O:34][C@@H:5]1[Br:44])[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1
Reactant: CC(=O)OC1O[C@H](COCc2ccccc2)[C@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@H]1OCc1ccccc1
Reactant: Br
Agent: O=C([O-])O
Agent: [Na+]
Solvent: Cc1ccccc1
Solvent: CC(C)OC(C)C
Product: Br[C@H]1O[C@H](COCc2ccccc2)[C@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@H]1OCc1ccccc1
Temperature: -5 °C
Reaction time: 1.5 h

Procedure:
2,3,4,6 -tetra-O-benzyl-D-galactopyranosyl acetate (79.8 g) was dissolved in the mixed solvent of toluene (160 ml) and isopropyl ether (520 ml), and cooled to a temperature in the range of −10-0° C. An isopropyl ether solution containing 2.0 equivalents of HBr (2.8 mmole/ml, ca. 100 ml) was added to this mixture. After stirring at −10-0° C. for about 90 minutes, unreacted HBr in the reaction mixture was neutralized with 5% aqueous sodium hydrogen carbonate solution. The total volume of the mixture was separated in a separatory funnel, the aqueous layer was discarded, and the organic layer was washed twice with 10% aqueous sodium chloride solution, and concentrated under reduced pressure to give 2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl bromide (GalBr) in the form of syrup.
Reaction SMILES: Cl[C:2]1[C:11]2[C:6](=[CH:7][C:8]([O:14][CH3:15])=[C:9]([O:12][CH3:13])[CH:10]=2)[CH:5]=[C:4]([NH:16][C:17]2[CH:21]=[C:20]([CH:22]3[CH2:24][CH2:23]3)[NH:19][N:18]=2)[N:3]=1.[CH2:25]([OH:27])[CH3:26]>>[CH:22]1([C:20]2[NH:19][N:18]=[C:17]([NH:16][C:4]3[N:3]=[C:2]([O:27][CH2:25][CH3:26])[C:11]4[C:6]([CH:5]=3)=[CH:7][C:8]([O:14][CH3:15])=[C:9]([O:12][CH3:13])[CH:10]=4)[CH:21]=2)[CH2:24][CH2:23]1
Reactant: CCO
Reactant: COc1cc2cc(Nc3cc(C4CC4)[nH]n3)nc(Cl)c2cc1OC
Product: CCOc1nc(Nc2cc(C3CC3)[nH]n2)cc2cc(OC)c(OC)cc12

Procedure:
Similar procedure as described in example 10 was used, starting from (1-Chloro-6,7-dimethoxy-isoquinolin-3-yl)-(5-cyclopropyl-1H-pyrazol-3-yl)-amine and ethanol to give (5-Cyclopropyl-1H-pyrazol-3-yl)-(1-ethoxy-6,7-dimethoxy-isoquinolin-3-yl)-amine LC-MS m/e 355(MH+).