Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[C:6]([NH2:8])[C:5]([NH2:9])=[CH:4][C:3]=1[N:10]1[CH:14]=[CH:13][CH:12]=[CH:11]1.[C:15](OCC)(=[O:21])[C:16](OCC)=[O:17]>>[Cl:1][C:2]1[CH:7]=[C:6]2[C:5]([NH:9][C:15](=[O:21])[C:16](=[O:17])[NH:8]2)=[CH:4][C:3]=1[N:10]1[CH:14]=[CH:13][CH:12]=[CH:11]1
Reactant: Nc1cc(Cl)c(-n2cccc2)cc1N
Reactant: CCOC(=O)C(=O)OCC
Product: O=c1[nH]c2cc(Cl)c(-n3cccc3)cc2[nH]c1=O

Procedure:
0.6 g (2.9 mmol) of N-(2-chloro-4,5-diaminophenyl)pyrrole and 32 g (221 mmol) of diethyl oxalate were refluxed for 3 hours. The reaction mixture was cooled and then the crude product was filtered off and washed with petroleum ether.
Reaction SMILES: [CH:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[S:10][C:11]1[CH:16]=[CH:15][C:14]([C:17]2[N:22]=[CH:21][N:20]=[C:19](O)[CH:18]=2)=[CH:13][C:12]=1[C:24]([F:27])([F:26])[F:25])([CH3:3])[CH3:2].O=P(Cl)(Cl)[Cl:30]>>[Cl:30][C:19]1[CH:18]=[C:17]([C:14]2[CH:15]=[CH:16][C:11]([S:10][C:5]3[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=3[CH:1]([CH3:3])[CH3:2])=[C:12]([C:24]([F:26])([F:25])[F:27])[CH:13]=2)[N:22]=[CH:21][N:20]=1
Reactant: CC(C)c1ccccc1Sc1ccc(-c2cc(O)ncn2)cc1C(F)(F)F
Reactant: O=P(Cl)(Cl)Cl
Product: CC(C)c1ccccc1Sc1ccc(-c2cc(Cl)ncn2)cc1C(F)(F)F
Yield: 51 %

Procedure:
Then, 4-chloro-6-(4-(2-isopropyl-phenylsulfanyl)-3-trifluoromethyl-phenyl)-pyrimidine 47 was prepared as follows. Compound 46 (1.40 g, 3.59 mmol) was treated with POCl3 (30 mL) at 60° C. for an hour. The reaction mixture was concentrated on a rotor-vapor, and the residue was treated with crushed ice (10 g). Water (50 mL) was added. The aqueous solution was then extracted with ethyl acetate (2×50 mL). The combined organic layers were washed with brine (3×50 mL), dried over MgSO4, filtered and concentrated. The crude product was purified by chromatography to give a brown oil 47 (0.74 g, 51%). 1H-NMR (CDCl3, 400 MHz) δ 1.19 (d, J=6.7 Hz, 6H), 3.50 (heptet, J=6.8 Hz, 1H), 6.89 (d, J=8.5 Hz, 1H), 7.24-7.28 (m, 1H), 7.46-7.50 (m, 2H), 7.54 (d, J=7.6 Hz, 1H), 7.68 (s, 1H), 7.93 (d, J=8.4 Hz, 1H), 8.38 (s, 1H), 9.00(s, 1H), MS (DCI) m/z 409, 411 (M+H)+.
Reaction SMILES: Cl.Cl.[O:3]1[C:11]2[CH:10]=[CH:9][N:8]=[CH:7][C:6]=2[C:5]([N:12]2[CH2:17][CH2:16][N:15]([CH2:18][CH2:19][C@H:20]3[CH2:25][CH2:24][C@H:23]([NH2:26])[CH2:22][CH2:21]3)[CH2:14][CH2:13]2)=[N:4]1.[CH3:27][C:28](O)=[O:29].CCN(C(C)C)C(C)C.CN(C(ON1N=NC2C=CC=CC1=2)=[N+](C)C)C.[B-](F)(F)(F)F>O1CCOCC1>[O:3]1[C:11]2[CH:10]=[CH:9][N:8]=[CH:7][C:6]=2[C:5]([N:12]2[CH2:13][CH2:14][N:15]([CH2:18][CH2:19][C@H:20]3[CH2:25][CH2:24][C@H:23]([NH:26][C:28](=[O:29])[CH3:27])[CH2:22][CH2:21]3)[CH2:16][CH2:17]2)=[N:4]1
Reactant: CC(=O)O
Reactant: N[C@H]1CC[C@H](CCN2CCN(c3noc4ccncc34)CC2)CC1
Agent: CN(C)C(On1nnc2ccccc21)=[N+](C)C
Agent: Cl
Agent: F[B-](F)(F)F
Solvent: CCN(C(C)C)C(C)C
Solvent: C1COCCO1
Product: CC(=O)N[C@H]1CC[C@H](CCN2CCN(c3noc4ccncc34)CC2)CC1

Procedure:
A mixture in dioxane (5 ml) of trans-4-[2-(4-isoxazolo[4,5-c]pyridin-3-yl-piperazin-1-yl)-ethyl]-cyclohexylamine dihydrochloride (100 mg, 0.25 mmol), AcOH (22 mg, 0.37 mmol), iPr2NEt (161 mg, 1.2 mmol) and TBTU (96 mg, 0.30 mmol) was stirred 16 h at r.t. After evaporation to dryness sat. aq. NaHCO3 was added and the product was extracted with 2 portions of CH2Cl2. The organic layers were directly loaded on a column. Flash chromatography (20 g SiO2, CH2Cl2/MeOH 100:0→90:10) yielded 62 mg (67%) of the title compound as white solid. m/z=372.2 ([M+H]+).