Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: C([O:8][C:9]1[CH:10]=[C:11]2[C:16](=[CH:17][CH:18]=1)[O:15][C:14]([CH3:20])([CH3:19])[C@@H:13]([OH:21])[C@@H:12]2[N:22]([CH3:27])[S:23]([CH3:26])(=[O:25])=[O:24])C1C=CC=CC=1.[H][H]>C1COCC1.CO.[Pd]>[OH:21][CH:13]1[CH:12]([N:22]([CH3:27])[S:23]([CH3:26])(=[O:24])=[O:25])[C:11]2[C:16](=[CH:17][CH:18]=[C:9]([OH:8])[CH:10]=2)[O:15][C:14]1([CH3:20])[CH3:19]
Reactant: [H][H]
Reactant: CN([C@@H]1c2cc(OCc3ccccc3)ccc2OC(C)(C)[C@H]1O)S(C)(=O)=O
Agent: [Pd]
Solvent: CO
Solvent: C1CCOC1
Product: CN(C1c2cc(O)ccc2OC(C)(C)C1O)S(C)(=O)=O
Yield: 89.3 %

Procedure:
1.0 g (2.6 mmol) of (±)-trans-N-(6-benzyloxy-3-hydroxy-2,2-dimethylchroman-4-yl)-N-methyl-methanesulfonamide (Example 1) was hydrogenated in 100 ml of THF/methanol (1:1) in the presence of palladium/carbon until the uptake of hydrogen had ended. The catalyst was filtered off and the filtrate was concentrated, giving 0.7 g of N-(3,6-dihydroxy-2,2-dimethylchroman-4-yl)-N-methyl-methanesulfonamide; m.p. 204-206° C.
Reaction SMILES: [CH2:1]([C:9]1[CH:21]=[CH:20][C:12]([CH2:13][CH2:14]CS([O-])(=O)=O)=[CH:11][CH:10]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[I-:22].[Na+]>O1CCCC1>[I:22][CH2:14][CH2:13][C:12]1[CH:20]=[CH:21][C:9]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])=[CH:10][CH:11]=1
Reactant: [I-]
Reactant: CCCCCCCCc1ccc(CCCS(=O)(=O)[O-])cc1
Agent: [Na+]
Solvent: C1CCOC1
Product: CCCCCCCCc1ccc(CCI)cc1
Reaction time: 0.17 h

Procedure:
4-Octylphenethylmethane sulfonate (70 g) and dry tetrahydrofuran (500 mL) are charged into a 1 liter single-neck round bottom flask, equipped with a calcium chloride guard tube and shielded with light protecting black cover. The mixture is stirred for 10 minutes, then sodium iodide (133 g) is added and the mixture is stirred overnight at room temperature. The solvent is evaporated under vacuum and the residue is dissolved in water (300 mL) and extracted with ethyl acetate (2×250 mL). Ethyl acetate extracts are combined, washed with aqueous sodium thiosulphate, dried with sodium sulphate, and concentrated under vacuum to give the title compound. Yield: 70 g.
Reaction SMILES: [N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]([OH:9])=[O:8].O=O.C(C1C=CC=CN=1)#N.N1C=CC=CC=1C(N)=[O:27]>>[OH:27][C:6]1[N:1]=[C:2]([C:7]([OH:9])=[O:8])[CH:3]=[CH:4][CH:5]=1
Reactant: O=C(O)c1ccccn1
Reactant: NC(=O)c1ccccn1
Agent: O=O
Solvent: N#Cc1ccccn1
Product: O=C(O)c1cccc(O)n1
Reaction time: 0.5 h

Procedure:
The biomass was cultured as described in Example 1. The formation of picolinic acid took place under strictly anaerobic conditions. A 500 ml glass bottle with rubber septum charged with 400 ml of biomass of OD650 =20 was used for the biotransformation. Incubation took place at 30° C. Before the biotransformation was started, the mixture was made anaerobic with pure nitrogen. For this purpose, nitrogen (50 mbar gauge pressure) was passed through a needle into the stirred mixture for about 30 minutes in order to drive out the oxygen quantitatively. In order to prevent oxygen from entering during the biotransformation or on addition of the 2-cyanopyridine, the gas introduction was maintained during the biotransformation (about 10 mbar gauge pressure). 2-cyanopyridine was added in 12 steps each of 10 g/l, in each case after one hour had elapsed. The addition can, however, also take place continuously. HPLC was used to check whether 2-cyanopyridine had been completely converted into picolinic acid before adding another portion. During the biotransformation there was no detectable formation of picolinamide. It was possible with this process to prepare about 150 g/l picolinic acid within 26 hours. 6-Hydroxypicolinic acid was not formed during this.
Reaction SMILES: Br.[Br:2][CH2:3][CH2:4][CH2:5][NH2:6].[O:7](C(OC(C)(C)C)=O)[C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=O.C([O-])([O-])=O.[K+].[K+]>C(O)C>[Br:2][CH2:3][CH2:4][CH2:5][NH:6][C:8](=[O:7])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12]
Reactant: NCCCBr
Reactant: CC(C)(C)OC(=O)OC(=O)OC(C)(C)C
Agent: Br
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CCO
Product: CC(C)(C)OC(=O)NCCCBr
Yield: 94.2 %

Procedure:
A solution of 3-bromopropylamine hydrobromide (10.9 g, 49.8 mmol), BOC2O (11.4 g, 52.3 mmol) and K2CO3 (20.6 g, 149.4 mmol) in ethanol (100 ml) were stirred at room temperature overnight. The precipitated salts were removed by filtration and the filtrate was concentrated in vacuo. The residue was dissolved in dichloromethane and washed with water, followed by brine. The organic layer was dried over MgSO4 and concentrated in vacuo to give 11.2 g (46.9 mmol, 94%) of the desired product: 1H NMR (400 MHz, CDCl3) δ 5.07 (br, 1H), 3.31 (t, 2H, J=6.6 Hz), 3.12 (apparent br q, 2H, J=6.0 Hz), 1.92 (quintet, 2H, J=6.6 Hz), 1.30 (s, 9H).
Reaction SMILES: CS[C:3]1[N:8]=[C:7]([C:9]2[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=2)[CH:6]=[CH:5][N:4]=1.O[O:16][S:17]([O-:19])=O.[K+].[C:21]([O-])(O)=O.[Na+]>CO>[CH3:21][S:17]([C:3]1[N:8]=[C:7]([C:9]2[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=2)[CH:6]=[CH:5][N:4]=1)(=[O:19])=[O:16]
Reactant: CSc1nccc(-c2cccnc2)n1
Reactant: O=C([O-])O
Reactant: O=S([O-])OO
Agent: [K+]
Agent: [Na+]
Solvent: CO
Product: CS(=O)(=O)c1nccc(-c2cccnc2)n1
Temperature: 25 °C
Reaction time: 1.5 h
Yield: 61 %

Procedure:
A solution of 2-methylsulfanyl-4-pyridin-3-yl-pyrimidine (1.18 g, 5.81 mmol) in MeOH (45 ml) was cooled at 0° C., then an aqueous solution of oxone (10.7 g, 17.45 mmol in 45 ml of water) was slowly added. After stirring 1.5 hours at room temperature, the mixture was basified with 5% NaHCO3 and the product was extracted with ethyl acetate. The organic phase was dried (Na2SO4) and evaporated to give 846 mg of the title compound that was used in the next step without further purification (61% yield).
Reaction SMILES: [CH3:1][O:2][C:3]([C:5]1[CH2:10][CH2:9][C:8](=[O:11])[NH:7][C:6]=1[C:12](=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:4].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[CH3:13][CH2:12][CH2:6][CH:5]([CH3:10])[CH3:3].[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8](=[O:11])[NH:7][C:6]=1[C:12](=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:4]
Reactant: COC(=O)C1=C(C(=O)c2ccccc2)NC(=O)CC1
Agent: N#CC1=C(C#N)C(=O)C(Cl)=C(Cl)C1=O
Solvent: Cc1ccccc1
Product: CCCC(C)C
Product: COC(=O)c1ccc(=O)[nH]c1C(=O)c1ccccc1
Reaction time: 24 h
Yield: 69.9 %

Procedure:
2-Benzoyl-6-oxo-1,4,5,6-tetrahydropyridine-3-carboxylic acid methyl ester (5.97 g) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 7.85 g) were stirred together at reflux in toluene (125 ml) for 24 h. More DDQ (7.85 g) was added and the mixture was stirred as before for a further 24 h. The solvent was removed in vacuo, and the residue was purified by flash chromatography on silica gel, eluting with 1:1 ethyl acetate:isohexane, yielding 2-benzoyl-6-oxo-1,6-dihydropyridine-3-carboxylic acid methyl ester as a brown solid (2.07 g). 1H NMR (400 MHz, CDCl3) δ3.54 (3H, s), 6.60 (1H, d, J=9.7 Hz), 7.50 (2H, t, J=7.8 Hz), 7.64 (1H, t, J=7.4 Hz), 7.82 (2H, d, J=8.2 Hz), 7.95 (1H, d, J=9.7 Hz), 11.00 (1H, br s); MS (ES+) m/e 258 [MH]+, 226 [M−OMe]+.