Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([C:8]([C:10]2[N:19]=[C:18]([NH:20][C:21]3[CH:25]=[C:24]([CH3:26])[NH:23][N:22]=3)[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[N:11]=2)=[O:9])[CH:5]=[CH:6][CH:7]=1.C1COCC1.CO.[BH4-].[Na+].Cl>CS(C)=O>[F:1][C:2]1[CH:3]=[C:4]([CH:8]([C:10]2[N:19]=[C:18]([NH:20][C:21]3[CH:25]=[C:24]([CH3:26])[NH:23][N:22]=3)[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[N:11]=2)[OH:9])[CH:5]=[CH:6][CH:7]=1
Reactant: Cc1cc(Nc2nc(C(=O)c3cccc(F)c3)nc3ccccc23)n[nH]1
Agent: Cl
Agent: [BH4-]
Agent: [Na+]
Solvent: C1CCOC1
Solvent: CS(C)=O
Solvent: CO
Product: Cc1cc(Nc2nc(C(O)c3cccc(F)c3)nc3ccccc23)n[nH]1
Temperature: 0 °C
Reaction time: 0.5 h
Yield: 33.3 %

Procedure:
To (3-fluorophenyl)(4-(5-methyl-1H-pyrazol-3-ylamino)quinazolin-2-yl)methanone from Example 1 (0.15 g, 0.43 mmol) in 1:1 THF/MeOH (4 mL) at 0° C. was added sodium borohydride (0.02 g, 0.58 mmol) and the mixture was stirred at 0° C. for 30 min. To the mixture were added 6 N HCl and DMSO (3 mL), and the mixture was purified by preparative HPLC (Varian diphenyl reverse phase column eluting with gradient of solvent B=0.05% HOAC/MeOH and solvent A=0.05% HOAc/H2O) to afford (3-fluorophenyl)(4-(5-methyl-1H-pyrazol-3-ylamino)quinazolin-2-yl)methanol (50 mg, 32%). 1H NMR (300 MHz, DMSO-d6) δ 2.26 (s, 3H) 5.7 (s, 1H) 5.93 (s, 1H) 6.44 (s, 1H) 7.07 (m, 1H) 7.34-7.39 (m, 3H) 7.54 (m, 1H) 7.81 (s, 2H) 8.59 (d, 1H) 10.42 (s, 1H) 12.15 (s, 1H); LC-MS (ESI) m/z 350 (M+H)+.
Reaction SMILES: C1(OC(=O)[N:9]([CH:42]2[CH2:44][CH2:43]2)[CH2:10][C:11]2[N:12]=[C:13]([C:32]3[CH:37]=[CH:36][C:35]([C:38]([F:41])([F:40])[F:39])=[CH:34][CH:33]=3)[S:14][C:15]=2[CH2:16][O:17][C:18]2[CH:23]=[CH:22][C:21]([C:24]3[NH:28][C:27](=[O:29])[O:26][N:25]=3)=[C:20]([O:30][CH3:31])[CH:19]=2)C=CC=CC=1.[OH-].[K+]>C(O)CO.O>[CH:42]1([NH:9][CH2:10][C:11]2[N:12]=[C:13]([C:32]3[CH:33]=[CH:34][C:35]([C:38]([F:40])([F:41])[F:39])=[CH:36][CH:37]=3)[S:14][C:15]=2[CH2:16][O:17][C:18]2[CH:23]=[CH:22][C:21]([C:24]3[NH:28][C:27](=[O:29])[O:26][N:25]=3)=[C:20]([O:30][CH3:31])[CH:19]=2)[CH2:43][CH2:44]1
Reactant: COc1cc(OCc2sc(-c3ccc(C(F)(F)F)cc3)nc2CN(C(=O)Oc2ccccc2)C2CC2)ccc1-c1noc(=O)[nH]1
Agent: [K+]
Agent: [OH-]
Solvent: O
Solvent: OCCO
Product: COc1cc(OCc2sc(-c3ccc(C(F)(F)F)cc3)nc2CNC2CC2)ccc1-c1noc(=O)[nH]1
Yield: 35.9 %

Procedure:
To a solution of 32.6 mg of cyclopropyl-[5-[3-methoxy-4-(5-oxo-4,5-dihydro-[1,2,4]oxadiazol-3-yl)-phenoxymethyl]-2-(4-trifluoromethyl-phenyl)-thiazol-4-ylmethyl]-carbamic acid phenyl ester in 2 mL of ethylene glycol was added 2 mL of a saturated solution of potassium hydroxide in water. The resulting mixture was stirred in a sealed tube under microwave irradiation for 25 minutes to 100° C., then 10 additional minutes to 120° C. and finally 15 more minutes to 140° C. It was then extracted with dichloromethane. The organic extracts were washed water, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (gradient from dichloromethane 100 to dichloromethane 90/methanol 10) to give 9.5 mg of 3-{4-[4-cyclopropylaminomethyl-2-(4-trifluoromethyl-phenyl)-thiazol-5-ylmethoxy]-2-methoxy-phenyl}-4H-[1,2,4]oxadiazol-5-one.
Reaction SMILES: [N:1]([CH2:4][CH2:5][C:6]1[C:14]2[C:9](=[CH:10][C:11]([Cl:16])=[C:12]([Cl:15])[CH:13]=2)[NH:8][C:7]=1[Si](CC)(CC)CC)=[N+]=[N-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CO>[Cl:15][C:12]1[CH:13]=[C:14]2[C:9](=[CH:10][C:11]=1[Cl:16])[NH:8][CH:7]=[C:6]2[CH2:5][CH2:4][NH2:1]
Reactant: CC[Si](CC)(CC)c1[nH]c2cc(Cl)c(Cl)cc2c1CCN=[N+]=[N-]
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: CO
Product: NCCc1c[nH]c2cc(Cl)c(Cl)cc12
Temperature: 70 °C
Reaction time: 2 h

Procedure:
A mixture of 3-(2-azidoethyl)-5,6-dichloro-2-(triethylsilyl)-1H-indole (0.497 g; 1.35 mmol) and triphenylphosphine (0.529 g; 1.35 mmol) in methanol (10 mL) was stirred at 70° C. for 2 hours. The reaction mixture was concentrated under reduced pressure and the crude material was dissolved in a solution of tetrabutylamonium fluoride (4.04 mL 1M) in THF, stirred at room temperature for 36 hours, and concentrated under reduced pressure. The crude material was used without any further purification.
Reaction SMILES: C([O:4][CH2:5][C:6]([NH:8][C:9]1[CH:16]=[CH:15][CH:14]=[C:13]([N:17]2[CH2:22][CH2:21][O:20][CH2:19][CH2:18]2)[C:10]=1[C:11]#[N:12])=[O:7])(=O)C.N>CO>[OH:4][CH2:5][C:6]([NH:8][C:9]1[CH:16]=[CH:15][CH:14]=[C:13]([N:17]2[CH2:18][CH2:19][O:20][CH2:21][CH2:22]2)[C:10]=1[C:11]#[N:12])=[O:7]
Reactant: CC(=O)OCC(=O)Nc1cccc(N2CCOCC2)c1C#N
Agent: N
Solvent: CO
Product: N#Cc1c(NC(=O)CO)cccc1N1CCOCC1
Temperature: 25 °C
Reaction time: 1 h
Yield: 54.2 %

Procedure:
To a solution of 2-(acetoxyacetylamino)-6-morpholinobenzonitrile (3 g) in methanol (200 ml) is added dropwise 28% aqueous ammonia (10 ml). The mixture is stirred at room temperature for 1 hour, and thereafter, the solvent is distilled off under reduced pressure. The resulting residue is recrystallized from ethanol-water to give the title compound (1.4 g) having the following physical properties.
Reaction SMILES: [Cl:1][C:2]1[C:3]([OH:40])=[C:4]([S:9]([N:12]([CH2:26][C:27]2[CH:32]=[CH:31][C:30]([C:33]3[CH:38]=[CH:37][C:36]([F:39])=[CH:35][CH:34]=3)=[CH:29][CH:28]=2)[CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[C:16]([CH2:20][NH:21][CH2:22][CH:23]([CH3:25])[CH3:24])[CH:15]=2)(=[O:11])=[O:10])[CH:5]=[C:6]([Cl:8])[CH:7]=1.[CH:41]1[CH:46]=[CH:45][C:44]([C:47]2[C:52]([N:53]=[C:54]=[O:55])=[CH:51][CH:50]=[CH:49][CH:48]=2)=[CH:43][CH:42]=1>C1COCC1>[C:47]1([C:44]2[CH:45]=[CH:46][CH:41]=[CH:42][CH:43]=2)[CH:48]=[CH:49][CH:50]=[CH:51][C:52]=1[NH:53][C:54](=[O:55])[N:21]([CH2:20][C:16]1[CH:15]=[C:14]([CH:19]=[CH:18][CH:17]=1)[CH2:13][N:12]([CH2:26][C:27]1[CH:32]=[CH:31][C:30]([C:33]2[CH:34]=[CH:35][C:36]([F:39])=[CH:37][CH:38]=2)=[CH:29][CH:28]=1)[S:9]([C:4]1[CH:5]=[C:6]([Cl:8])[CH:7]=[C:2]([Cl:1])[C:3]=1[OH:40])(=[O:11])=[O:10])[CH2:22][CH:23]([CH3:25])[CH3:24]
Reactant: CC(C)CNCc1cccc(CN(Cc2ccc(-c3ccc(F)cc3)cc2)S(=O)(=O)c2cc(Cl)cc(Cl)c2O)c1
Reactant: O=C=Nc1ccccc1-c1ccccc1
Solvent: C1CCOC1
Product: CC(C)CN(Cc1cccc(CN(Cc2ccc(-c3ccc(F)cc3)cc2)S(=O)(=O)c2cc(Cl)cc(Cl)c2O)c1)C(=O)Nc1ccccc1-c1ccccc1
Temperature: 25 °C
Reaction time: 0.25 h
Yield: 56.4 %

Procedure:
To a solution of 3,5-dichloro-N-((4′-fluorobiphenyl-4-yl)methyl)-2-hydroxy-N-(3-((isobutyl amino)methyl)benzyl)benzene sulfonamide (Compound E of Example 184, 0.04 g, 0.0667 mmol, 1.0 eq) in a 5 mL of THF at 0° C. was added 2-biphenyl isocyanate (0.013 g, 0.0667 mmol, 1.0 eq). The reaction mixture was stirred at ambient temperature for 15 min and concentrated to remove the volatiles. The residue was purified by preparative HPLC to afford the title compound (0.03 g, 60%). 1H NMR (400 MHz, DMSO-d6) δ 0.66-0.68 (d, 6H), 1.7 (m, 1H), 2.82-2.84 (d, 2H), 4.30 (s, 2H), 4.43 (d, 4H), 6.84-6.89 (t, 2H), 6.99 (d, 1H), 7.14-7.20 (m, 4H), 7.23 (m, 4H), 7.25-7.34 (m, 5H), 7.44-7.46 (d, 3H), 7.57-7.62 (m, 4H), 7.80 (s, 1H). MS (HD: 796.1 (M−H)−.