Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [N:1]1[CH:6]=[CH:5][CH:4]=[N:3][C:2]=1[N:7]1[CH2:12][CH2:11][N:10]([CH2:13][CH2:14][CH2:15][C:16]#[N:17])[CH2:9][CH2:8]1.NN>C(O)(C)C.[Ni].C(O)C>[NH2:17][CH2:16][CH2:15][CH2:14][CH2:13][N:10]1[CH2:9][CH2:8][N:7]([C:2]2[N:1]=[CH:6][CH:5]=[CH:4][N:3]=2)[CH2:12][CH2:11]1
Reactant: N#CCCCN1CCN(c2ncccn2)CC1
Agent: [Ni]
Agent: NN
Solvent: CCO
Solvent: CC(C)O
Product: NCCCCN1CCN(c2ncccn2)CC1
Yield: 68.1 %

Procedure:
4-[4-(2-Pyrimidinyl)-1-piperazinyl]butyronitrile (115.7 g; 0.5 mole) was dissolved in 1.5 L isopropyl alcohol. Approximately 50 mL of a suspension of Raney nickel in anhydrous ethanol was added and the resulting reaction mixture was heated to reflux and hydrazine (120 g) was slowly added dropwise. On completion of the reaction, the spent catalyst was removed by filtration and the filtrate was concentrated in vacuo to a yellow oil which was distilled to yield 80.1 g (60%) of product, boiling point 135°-145° C. at 0.10 mm. (The nitrile used in this reaction is described in Wu, et al., Journal of Medicinal Chemistry, 15, page 477-479 (1972).)
Reaction SMILES: [Br:1][CH2:2][CH2:3]Br.[Cl:5][C:6]1[CH:7]=[C:8]([NH:13][C:14](=[O:28])[CH2:15][O:16][C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][C:18]=2[Cl:27])[CH:9]=[CH:10][C:11]=1[OH:12].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[Br:1][CH2:2][CH2:3][O:12][C:11]1[CH:10]=[CH:9][C:8]([NH:13][C:14](=[O:28])[CH2:15][O:16][C:17]2[CH:22]=[CH:21][C:20]([C:23]([F:24])([F:25])[F:26])=[CH:19][C:18]=2[Cl:27])=[CH:7][C:6]=1[Cl:5]
Reactant: O=C(COc1ccc(C(F)(F)F)cc1Cl)Nc1ccc(O)c(Cl)c1
Reactant: BrCCBr
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CN(C)C=O
Product: O=C(COc1ccc(C(F)(F)F)cc1Cl)Nc1ccc(OCCBr)c(Cl)c1
Reaction time: 2.5 h

Procedure:
A solution of 3.66 mL (41.56 mmol) 1,2-dibromoethane in 5 mL DMF was slowly added at RT to a suspension of 1.580 g (4.156 mmol) N-(3-chloro-4-hydroxy-phenyl)-2-(2-chloro-4-trifluoromethyl-phenoxy)-acetamide and 2.880 g (8.310 mmol) potassium carbonate in 20 mL DMF and the mixture was stirred for 2.5 h. The reaction mixture was evaporated down i. vac. and diluted with EtOAc . The org. phase was washed with water and saturated aqueous NaCl, dried over magnesium sulphate and evaporated down i. vac. Column chromatography (silica gel, petroleum ether→dichloromethane) yielded the product.
Reaction SMILES: [Cl:1][C:2]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([Cl:13])[C:3]=1[CH2:4][OH:5].N1C=CN=C1.[Si:19](Cl)([C:32]([CH3:35])([CH3:34])[CH3:33])([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CN(C)C=O.O>[Si:19]([O:5][CH2:4][C:3]1[C:6]([Cl:13])=[CH:7][CH:8]=[C:9]([N+:10]([O-:12])=[O:11])[C:2]=1[Cl:1])([C:32]([CH3:35])([CH3:34])[CH3:33])([C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1
Reactant: CC(C)(C)[Si](Cl)(c1ccccc1)c1ccccc1
Reactant: O=[N+]([O-])c1ccc(Cl)c(CO)c1Cl
Agent: c1c[nH]cn1
Solvent: O
Solvent: CN(C)C=O
Product: CC(C)(C)[Si](OCc1c(Cl)ccc([N+](=O)[O-])c1Cl)(c1ccccc1)c1ccccc1
Reaction time: 8 h

Procedure:
To a solution of 2,6-dichloro-3-nitrobenzyl alcohol (5.0 g) in N,N-dimethylformamide (25 ml) were added imidazole (1.69 g) and tert-butyldiphenylsilyl chloride (6.0 ml) at ambient temperature with stirring. After 8 hours, the mixture was diluted with water (25 ml) and was extracted with ethyl acetate twice. The organic layer was washed with water and brine, dried over magnesium sulfate. The solvent was removed in vacuo to give 1-(tert-butyldiphenylsilyloxy-methyl)-2,6-dichloro-3-nitrobenzene (11.5 g) as an oil.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH3:9])[CH:6]=[CH:5][C:4]=1[C:10]([CH3:21])([CH3:20])[CH2:11][C:12]([OH:19])([C:15]([F:18])([F:17])[F:16])[CH:13]=O.[NH2:22][C:23]1[CH:32]=[CH:31][CH:30]=[C:29]2[C:24]=1[CH:25]=[N:26][NH:27][C:28]2=[O:33]>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[OH:19][C:12]1([C:15]([F:16])([F:18])[F:17])[CH2:11][C:10]([CH3:20])([CH3:21])[C:4]2[C:5](=[CH:6][C:7]([CH3:9])=[CH:8][C:3]=2[O:2][CH3:1])[CH:13]1[NH:22][C:23]1[CH:32]=[CH:31][CH:30]=[C:29]2[C:24]=1[CH:25]=[N:26][NH:27][C:28]2=[O:33]
Reactant: Nc1cccc2c(=O)[nH]ncc12
Reactant: COc1cc(C)ccc1C(C)(C)CC(O)(C=O)C(F)(F)F
Agent: Cl[Ti](Cl)(Cl)Cl
Solvent: ClCCl
Product: COc1cc(C)cc2c1C(C)(C)CC(O)(C(F)(F)F)C2Nc1cccc2c(=O)[nH]ncc12
Yield: 10.9 %

Procedure:
Analogously to Example 10, the corresponding imine is produced starting from 500 mg of 4-(2-methoxy-4-methylphenyl)-2-hydroxy-4-methyl-2-(trifluoromethyl)pentanal and 287 mg of 5-amino-phthalazin-1-one. As in Example 3, 320 mg of the imine is reacted by reaction with 7.2 ml of titanium tetrachloride (1 M in dichloromethane) in 20 ml of dichloromethane, and 80 mg of the title compound is obtained.
Reaction SMILES: C(OC([N:8]1[CH2:13][CH2:12][CH:11]([C:14]2[O:15][C:16]([C:19]3[C:20]([NH2:35])=[N:21][CH:22]=[C:23]([C:25]4[CH:26]=[C:27]5[C:31](=[CH:32][CH:33]=4)[N:30]([CH3:34])[CH:29]=[CH:28]5)[CH:24]=3)=[N:17][N:18]=2)[CH2:10][CH2:9]1)=O)(C)(C)C.C([SiH](CC)CC)C.C([O-])(O)=O.[Na+]>C(O)(C(F)(F)F)=O.O>[CH3:34][N:30]1[C:31]2[C:27](=[CH:26][C:25]([C:23]3[CH:24]=[C:19]([C:16]4[O:15][C:14]([CH:11]5[CH2:12][CH2:13][NH:8][CH2:9][CH2:10]5)=[N:18][N:17]=4)[C:20]([NH2:35])=[N:21][CH:22]=3)=[CH:33][CH:32]=2)[CH2:28][CH2:29]1
Reactant: Cn1ccc2cc(-c3cnc(N)c(-c4nnc(C5CCN(C(=O)OC(C)(C)C)CC5)o4)c3)ccc21
Agent: CC[SiH](CC)CC
Agent: O=C([O-])O
Agent: [Na+]
Solvent: O
Solvent: O=C(O)C(F)(F)F
Product: CN1CCc2cc(-c3cnc(N)c(-c4nnc(C5CCNCC5)o4)c3)ccc21
Temperature: 0 °C
Reaction time: 2 h

Procedure:
To a solution of 4-{5-[2-amino-5-(1-methyl-1H-indol-5-yl)-pyridin-3-yl]-[1,3,4]oxadiazol-2-yl}-piperidine-1-carboxylic acid tert-butyl ester (300 mg, 0.63 mmol) in TFA (2.0 mL) at 0° C. was added triethylsilane (146 mg, 1.26 mmol) drop-wise over a period of 5 min, and stirred for 2 h at 0° C. The reaction was diluted with water (20 mL), neutralized with saturated aqueous NaHCO3 solution and extracted with ethyl acetate (3×20 mL). The organic layer was washed with brine, dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain crude product. Crude product was purified by washing with diethyl ether and hexane to afford the title compound as a yellow solid: