Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [C:1]1([P:7]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:8]2[CH:9]=[CH:10][CH:11]=[C:12]3[C:17]=2[NH:16][CH:15]([CH3:18])[CH:14]=[CH:13]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.OO.[O-:27]S([O-])=O.[Na+].[Na+]>C(Cl)Cl>[C:19]1([P:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)([C:8]2[CH:9]=[CH:10][CH:11]=[C:12]3[C:17]=2[NH:16][CH:15]([CH3:18])[CH:14]=[CH:13]3)=[O:27])[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1
Reactant: O=S([O-])[O-]
Reactant: CC1C=Cc2cccc(P(c3ccccc3)c3ccccc3)c2N1
Agent: OO
Agent: [Na+]
Solvent: ClCCl
Product: CC1C=Cc2cccc(P(=O)(c3ccccc3)c3ccccc3)c2N1
Temperature: 25 °C
Reaction time: 1 h

Procedure:
To a solution of 8-diphenylphosphino-2-methyl-1,2-dihydroquinoline (2) (10.5 g, 32 mmol) in CH2Cl2 (100 mL) was added H2O2 (6.6 mL, 30% w/w in H2O, 63.9 mmol) at 0° C. and the solution was stirred at room temperature for 1 hour. The solution was then cooled to 0° C., saturated aqueous Na2SO3 solution (10 mL) was added and the mixture was warmed to room temperature. Products were extracted with EtOAc, washed with water and saturated aqueous NaCl, dried (MgSO4) and evaporated to give 5 as a yellow oil (11 g, quantitative). 1H NMR (400.13 MHz, CDCl3) δ 7.7-7.6 (m, 4H, Ph-H), 7.6-7.5 (m, 2H, Ph-H), 7.5-7.4 (m, 4H, Ph-H), 6.97 (bs, 1H, N1—H), 6.87 (d, 1H, J=7.2 Hz, C5—H), 6.55 (ddd, 1H, J=14.0, 8.0, 1.6 Hz, C7—H), 6.36 (ddd, 1H, J=10.0, 7.6, 2.8 Hz, C6—H), 6.22 (d, 1H, J=10.0 Hz, C4—H), 5.51 (ddd, 1H, J=10.0, 4.0, 2.0 Hz, C3—H), 4.43 (m, 1H, C2—H), 1.17 (d, 3H, J=6.8 Hz, C1—CH3) ppm; 13C NMR (100.61 MHz, CDCl3) δ 148.2 (d, J=5.1 Hz), 146.0 (d, J=6.1 Hz), 135.7 (d, J=8.1 Hz), 134.8, 132.4, 131.3 (d, J=5.1 Hz), 131.0 (d, J=11.1 Hz), 130.8 (d, J=10.1 Hz), 130.7 (d, J=10.1 Hz), 130.1, 129.2, 127.2 (d, J=12.1 Hz), 126.6 (d, J=13.1 Hz), 126.3, 125.0 (d, J=8.1 Hz), 124.1 (d, J=13.1 Hz), 122.8, 121.1, 119.7 (d, J=8.1 Hz), 113.6 (d, J=14.1 Hz), 107.3, 106.2, 46.9, 23.5 ppm; 31P NMR (161.97 MHz, CDCl3) δ 36.0 ppm.
Reaction SMILES: [CH3:1][CH:2]([CH2:6][CH3:7])[CH:3]([OH:5])[CH3:4].[H-].[Na+].Cl[C:11]1[CH:12]=[CH:13][C:14]2[CH2:15][N:16]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:17][CH2:18][O:19][C:20]=2[N:21]=1.O>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH3:4][CH:3]([O:5][C:11]1[CH:12]=[CH:13][C:14]2[CH2:15][N:16]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:17][CH2:18][O:19][C:20]=2[N:21]=1)[CH:2]([CH3:1])[CH2:6][CH3:7]
Reactant: CCC(C)C(C)O
Reactant: CC(C)(C)OC(=O)N1CCOc2nc(Cl)ccc2C1
Agent: [Pd]
Agent: O=C(/C=C/c1ccccc1)/C=C/c1ccccc1
Agent: [H-]
Solvent: Cc1ccccc1
Solvent: O
Product: CCC(C)C(C)Oc1ccc2c(n1)OCCN(C(=O)OC(C)(C)C)C2
Temperature: 70 °C
Reaction time: 0.25 h
Yield: 61 %

Procedure:
To a solution of 3-methylpentan-2-ol (0.18 mL) in toluene (4 mL) was added sodium hydride (0.14 g), and the resulting mixture was stirred at 70° C. for 15 min under a nitrogen atmosphere. A mixture of tert-butyl 8-chloro-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.50 g), BINAP (0.033 g), Pd2(dba)3 (0.024 g) and toluene (4 mL) was added, and the resulting mixture was stirred at 100° C. for 2 hr under an argon atmosphere. The reaction solution was poured into water, and the resulting product was extracted with ethyl acetate. The organic layer was washed with water and saturated brine and dried, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 0→40% ethyl acetate/hexane) to give tert-butyl 8-(1,2-dimethylbutoxy)-2,3-dihydropyrido[3,2-f][1,4]oxazepine-4(5H)-carboxylate (0.37 g, 61%) as a yellow oil.
Reaction SMILES: [Cl:1][C:2]1[N:7]=[CH:6][C:5]([C:8]2[CH2:9][CH2:10][C:11](=[O:14])[NH:12][N:13]=2)=[CH:4][CH:3]=1.IC.[C:17](=O)([O-])[O-].[Cs+].[Cs+]>CS(C)=O.ClCCl>[Cl:1][C:2]1[N:7]=[CH:6][C:5]([C:8]2[CH:9]=[CH:10][C:11](=[O:14])[N:12]([CH3:17])[N:13]=2)=[CH:4][CH:3]=1
Reactant: O=C1CCC(c2ccc(Cl)nc2)=NN1
Reactant: O=C([O-])[O-]
Agent: [Cs+]
Solvent: CI
Solvent: CS(C)=O
Solvent: ClCCl
Product: Cn1nc(-c2ccc(Cl)nc2)ccc1=O
Temperature: 100 °C
Reaction time: 8 h
Yield: 76.4 %

Procedure:
To 6-(6-chloropyridin-3-yl)-4,5-dihydro-2H-pyridazin-3-one (1.03 g, 4.93 mmol) in DMSO (40 mL) was added iodomethane (460 μL, 7.4 mmol) and cesium carbonate (3.2 g, 9.86 mmol). After overnight stirring at 100° C. open to air, the reaction was cooled, diluted with dichloromethane, washed several times with water/brine, dried over sodium sulfate, and concentrated under vacuum to obtain 835 mg product (79%); MS m/z 222 (M+H).
Reaction SMILES: [CH3:1][O:2][C:3]([C:5]1[C:10]([CH3:11])=[C:9]([NH:12]C(=O)C)[CH:8]=[C:7]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([O:23][CH3:24])[C:17]=2[F:25])[N:6]=1)=[O:4].C(Cl)(=O)C>CO>[CH3:1][O:2][C:3]([C:5]1[C:10]([CH3:11])=[C:9]([NH2:12])[CH:8]=[C:7]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[C:18]([O:23][CH3:24])[C:17]=2[F:25])[N:6]=1)=[O:4]
Reactant: COC(=O)c1nc(-c2ccc(Cl)c(OC)c2F)cc(NC(C)=O)c1C
Solvent: CO
Solvent: CC(=O)Cl
Product: COC(=O)c1nc(-c2ccc(Cl)c(OC)c2F)cc(N)c1C
Temperature: 25 °C
Reaction time: 8 h
Yield: 89.9 %

Procedure:
4-Acetylamino-6-(4-chloro-2-fluoro-3-methoxyphenyl)-3-methylpyridine-2-carboxylic acid methyl ester (369 mg, 1.0 mmol) was dissolved in methanol (10 mL) and acetyl chloride (1.07 mL, 15 mmol) was added. The reaction mixture was stirred overnight at ambient temperature and concentrated under vacuum. The residue was partitioned between ethyl acetate and aqueous sodium bicarbonate; and the organic phase was dried and concentrated. Purification by flash chromatography on silica gel (dichloromethane/ethyl acetate gradient) followed by a second purification by flash chromatography (hexane/ethyl acetate gradient) yielded the title compound (292 mg, 88% yield) as a white solid, mp 122-125° C. 1H NMR (CDCl3) δ 7.65 (m, 1H), 7.26 (s, 1H), 7.1 (m, 1H), 4.35 (br s, 2H), 3.99 (s, 3H), 3.98 (d, 3H), 2.31 (s, 3H).
Reaction SMILES: [Cl:1][C:2]1[N:7]=[C:6]([CH2:8][OH:9])[C:5]2[C:10]([O:32][CH3:33])=[N:11][N:12]([C:13]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)([C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:4]=2[CH:3]=1.[CH3:34][NH:35][C:36](Cl)=[O:37].CCN(C(C)C)C(C)C>C(Cl)Cl>[CH3:34][NH:35][C:36](=[O:37])[O:9][CH2:8][C:6]1[C:5]2[C:10]([O:32][CH3:33])=[N:11][N:12]([C:13]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)([C:20]3[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=3)[C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:4]=2[CH:3]=[C:2]([Cl:1])[N:7]=1
Reactant: COc1nn(C(c2ccccc2)(c2ccccc2)c2ccccc2)c2cc(Cl)nc(CO)c12
Reactant: CNC(=O)Cl
Solvent: CCN(C(C)C)C(C)C
Solvent: ClCCl
Product: CNC(=O)OCc1nc(Cl)cc2c1c(OC)nn2C(c1ccccc1)(c1ccccc1)c1ccccc1
Temperature: 35 °C
Reaction time: 1 h
Yield: 76.3 %

Procedure:
A solution of (6-chloro-3-methoxy-1-trityl-1H-pyrazolo[4,3-c]pyridin-4-yl)methanol (Intermediate 35B, 200 mg, 0.439 mmol) and methylaminoformyl chloride (45.1 mg, 0.483 mmol) in DCM (1462 μl) was treated with DIEA (153 μl, 0.877 mmol) and stirred @ 35° C. for 1 h Reaction was dilluted in with DCM and concentrated in vacuo on silica. Material was purified by normal phase column chromotography eluting with Hex/EtOAc (0-40%) affording (6-chloro-3-methoxy-1-trityl-1H-pyrazolo[4,3-c]pyridin-4-yl)methyl methylcarbamate (172 mg, 0.335 mmol, 76% yield) as a white solid. MS: [M+H]+ m/z 513.
Reaction SMILES: [C:1]([Mg]Br)#[CH:2].[CH3:5][C:6](=[CH:9][CH2:10][CH:11]=[CH2:12])[CH:7]=[O:8]>O1CCCC1>[C:1]([CH:7]([OH:8])[C:6]([CH3:5])=[CH:9][CH2:10][CH:11]=[CH2:12])#[CH:2]
Reactant: C=CCC=C(C)C=O
Reactant: C#C[Mg]Br
Solvent: C1CCOC1
Product: C#CC(O)C(C)=CCC=C
Reaction time: 3 h
Yield: 401.1 %

Procedure:
To a solution of ethynyl magnesium bromide (prepared from 2.91 g of magnesium) in 100 ml of tetrahydrofuran, was added dropwise 11.0 g of 2-methyl-2,5-hexadienal at a temperature from 0° C to 10° C under cooling with ice-bath. The resulting reaction solution was stirred for 3 hours to complete the reaction and the same after-treatment as in the Reference Example 1 was then carried out to obtain 12.3 g of a colorless oily 1-ethynyl-2-methyl-2,5-hexadienyl alcohol, b.p. 60°-65° C/7 mmHg.
Reaction SMILES: [OH-].[K+].C[O:4][C:5]([C:7]1[CH:16]=[CH:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:17]([CH2:37][CH3:38])([C:20]3[CH:25]=[CH:24][C:23]([O:26][CH:27]([CH2:34][CH3:35])[CH:28]([OH:33])[C:29]([CH3:32])([CH3:31])[CH3:30])=[C:22]([CH3:36])[CH:21]=3)[CH2:18][CH3:19])[CH:13]=2)[CH:8]=1)=[O:6].C1COCC1.CO>O>[CH2:18]([C:17]([C:12]1[CH:13]=[C:14]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([C:5]([OH:6])=[O:4])[CH:16]=[CH:15]2)([C:20]1[CH:25]=[CH:24][C:23]([O:26][CH:27]([CH2:34][CH3:35])[CH:28]([OH:33])[C:29]([CH3:32])([CH3:30])[CH3:31])=[C:22]([CH3:36])[CH:21]=1)[CH2:37][CH3:38])[CH3:19]
Reactant: CCC(Oc1ccc(C(CC)(CC)c2ccc3cc(C(=O)OC)ccc3c2)cc1C)C(O)C(C)(C)C
Agent: [K+]
Agent: [OH-]
Solvent: C1CCOC1
Solvent: O
Solvent: CO
Product: CCC(Oc1ccc(C(CC)(CC)c2ccc3cc(C(=O)O)ccc3c2)cc1C)C(O)C(C)(C)C
Temperature: 60 °C
Reaction time: 14 h
Yield: 97.5 %

Procedure:
Add KOH (321 mg, 5.724 mmol) to a mixture of diastereomeric isomer pair 1 of 6-{1-ethyl-1-[4-(1-ethyl-2-hydroxy-3,3-dimethyl-butoxy)-3-methyl-phenyl]propyl}-naphthalene-2-carboxylic acid methyl ester (702 mg, 1.431 mmol), THF (9 ml), MeOH (3 ml), and H2O (1 ml). Heat the reaction mixture to 60° C. and stir it for 14 h. Cool and partition the reaction mixture between Et2O and 1N HCl. Dry the organic layer over MgSO4, filter, and concentrate the filter in vacuo to give the title compound as a glassy solid (665 mg, 97%). 1NMR (400 MHz, CDCl3) δ ppm: 0.64 (t, J=7.6 Hz, 6H), 0.93 (t, J=8.4 Hz, 3H), 0.93 (s, 9H), 1.72 (m, 1H), 1.82 (m, 1H), 2.12 (s, 3H), 2.19 (q, 4H), 3.28 (s, 1H), 4.28 (dd, J=6.0, 3.2 Hz, 1H), 6.65 (d, J=8.4 Hz, 1H), 6.90 (d, J=2.0 Hz, 1H), 6.94 (dd, J=6.0, 2.4 Hz, 1H), 7.21 (dd, J=7.2, 1.6 Hz, 1H), 7.78 (d, J=8.8 Hz, 1H), 7.86 (s, 1H), 7.89 (d, J=8.8 Hz, 1H), 8.09 (dd, J=6.8, 1.6 Hz, 1H), 8.62 (s, 1H). High Res. ES-MS: 499.2832; calc. for C31H40O4+Na: 499.2825.
Reaction SMILES: C([O:3][C:4]([C:6]1[NH:7][C:8]2[C:13]([CH:14]=1)=[CH:12][C:11]([Br:15])=[CH:10][CH:9]=2)=[O:5])C.Br[CH2:17][C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20][CH:19]=1>>[Br:15][C:11]1[CH:12]=[C:13]2[C:8](=[CH:9][CH:10]=1)[N:7]([CH2:17][C:18]1[C:27]3[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=3)[CH:21]=[CH:20][CH:19]=1)[C:6]([C:4]([OH:3])=[O:5])=[CH:14]2
Reactant: CCOC(=O)c1cc2cc(Br)ccc2[nH]1
Reactant: BrCc1cccc2ccccc12
Product: O=C(O)c1cc2cc(Br)ccc2n1Cc1cccc2ccccc12

Procedure:
Using general procedure B, 5-bromo-1H-indole-2-carboxylic acid ethyl ester was coupled with 1-bromomethyl-naphthalene and the product obtained was hydrolyzed to give the title compound as a white solid. MS: 380.1 ([M−H]−).
Reaction SMILES: [CH2:1]([O:3][C:4]([C:6]1([C:9]2[CH:14]=[CH:13][C:12]([C:15]3[CH:20]=[CH:19][C:18]([C:21]4[O:25][N:24]=[C:23]([CH3:26])[C:22]=4[CH:27]([OH:31])[CH2:28][CH:29]=[CH2:30])=[CH:17][CH:16]=3)=[CH:11][CH:10]=2)[CH2:8][CH2:7]1)=[O:5])[CH3:2].I[C:33]1[CH:38]=[CH:37][CH:36]=[C:35]([C:39]([F:42])([F:41])[F:40])[CH:34]=1>>[CH2:1]([O:3][C:4]([C:6]1([C:9]2[CH:10]=[CH:11][C:12]([C:15]3[CH:20]=[CH:19][C:18]([C:21]4[O:25][N:24]=[C:23]([CH3:26])[C:22]=4[CH:27]([OH:31])[CH2:28]/[CH:29]=[CH:30]/[C:33]4[CH:38]=[CH:37][CH:36]=[C:35]([C:39]([F:42])([F:41])[F:40])[CH:34]=4)=[CH:17][CH:16]=3)=[CH:13][CH:14]=2)[CH2:8][CH2:7]1)=[O:5])[CH3:2]
Reactant: FC(F)(F)c1cccc(I)c1
Reactant: C=CCC(O)c1c(C)noc1-c1ccc(-c2ccc(C3(C(=O)OCC)CC3)cc2)cc1
Product: CCOC(=O)C1(c2ccc(-c3ccc(-c4onc(C)c4C(O)C/C=C/c4cccc(C(F)(F)F)c4)cc3)cc2)CC1

Procedure:
Prepared according to the procedure described in Example 39, Step 1, using 1-{4′-[4-(1-hydroxy-but-3-enyl)-3-methyl-isoxazol-5-yl]-biphenyl-4-yl}-cyclopropanecarboxylic acid ethyl ester and 1-iodo-3-trifluoromethyl-benzene.
Reaction SMILES: [Br:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]([NH2:10])[CH3:9])=[CH:4][CH:3]=1.[CH3:11][S:12](Cl)(=[O:14])=[O:13].N1C=CC=CC=1>C(Cl)Cl>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]([NH:10][S:12]([CH3:11])(=[O:14])=[O:13])[CH3:9])=[CH:4][CH:3]=1
Reactant: CS(=O)(=O)Cl
Reactant: C[C@@H](N)c1ccc(Br)cc1
Solvent: c1ccncc1
Solvent: ClCCl
Product: C[C@@H](NS(C)(=O)=O)c1ccc(Br)cc1
Temperature: 25 °C
Reaction time: 3 h
Yield: 57.8 %

Procedure:
To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (0.5 g, 2.49 mmol), in anhydrous CH2Cl2 (5 mL) under argon were added methane sulfonyl chloride (0.23 mL, 2.99 mmol) and Pyridine (0.30 mL, 3.73 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1N HCl and extracted with EtOAc (30 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. 1H NMR (CDCl3) δ: 1.52 (d, J=6.8 Hz, 3H), 2.67 (s, 3H), 4.61-4.72 (m, 2H), 7.24 (d, J=8.3 Hz, 2H), 7.51 (d, J=8.3 Hz, 2H). ESIMS (MNa+): 279.
Reaction SMILES: [C:1]1([N:7]2[C:15](=[O:16])[C:14]3[C@@H:13]4[C:17]([CH3:19])([CH3:18])[C@@:10]([CH3:20])([CH2:11][CH2:12]4)[C:9]=3[NH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:21][O:22][CH2:23][CH2:24]Br.ClCCl.C>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O.CO.O>[CH3:21][O:22][CH2:23][CH2:24][N:8]1[C:9]2[C@@:10]3([CH3:20])[C:17]([CH3:19])([CH3:18])[C@H:13]([CH2:12][CH2:11]3)[C:14]=2[C:15](=[O:16])[N:7]1[C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1
Reactant: CC1(C)[C@@H]2CC[C@@]1(C)c1[nH]n(-c3ccccc3)c(=O)c12
Reactant: COCCBr
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: [I-]
Solvent: ClCCl
Solvent: CO
Solvent: O
Product: COCCn1c2c(c(=O)n1-c1ccccc1)[C@H]1CC[C@]2(C)C1(C)C
Temperature: 100 °C
Yield: 5.6 %

Procedure:
A mixture of (4S,7R)-7,8,8-trimethyl-2-phenyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 6; 150 mg, 0.56 mmol), tetrabutylammonium iodide (207 mg, 0.56 mmol) and 2-bromoethyl methyl ether (540 μL, 5.75 mmol) in dimethylformamide (3 mL) was heated in an oil-bath at 100° C. for 17 h. An additional portion of 2-bromoethyl methyl ether (540 μL, 5.75 mmol) was added and the mixture was heated at 100° C. for 3 days. Dichloromethane (75 mL) and water (25 mL) were added, and the aqueous layer was back-extracted with dichloromethane (2×30 mL). The combined organic layers were washed with water (4×20 mL), aqueous sodium thiosulfate (20 mL), and brine (30 mL). The solution was dried (magnesium sulfate), filtered, evaporated and the residue was purified using an ISCO 40 g column, eluting with 20-100% ethyl acetate/hexanes to give an orange oil. This was treated with charcoal in methanol and the mixture was filtered through Celite. The solvent was evaporated to give (4S,7R)-1-(2-methoxy-ethyl)-7,8,8-trimethyl-2-phenyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (10.3 mg, 6%) as an orange oil. The purity of the sample was assessed at 88% by 1H NMR. ES(+)-MS (M+H) 327.
Reaction SMILES: C(OC(=O)[NH:7][CH2:8][C:9]1[O:10][C:11]([C:14]2[CH:19]=[CH:18][C:17]([C@@H:20]([OH:30])[C@H:21]([NH:24][C:25](=[O:29])[CH:26]([Cl:28])[Cl:27])[CH2:22][F:23])=[CH:16][CH:15]=2)=[CH:12][N:13]=1)(C)(C)C.FC(F)(F)C(O)=O>C(Cl)Cl>[NH2:7][CH2:8][C:9]1[O:10][C:11]([C:14]2[CH:19]=[CH:18][C:17]([C@@H:20]([OH:30])[C@H:21]([NH:24][C:25](=[O:29])[CH:26]([Cl:27])[Cl:28])[CH2:22][F:23])=[CH:16][CH:15]=2)=[CH:12][N:13]=1
Reactant: CC(C)(C)OC(=O)NCc1ncc(-c2ccc([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)cc2)o1
Solvent: O=C(O)C(F)(F)F
Solvent: ClCCl
Product: NCc1ncc(-c2ccc([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)cc2)o1
Temperature: 25 °C
Reaction time: 2 h
Yield: 110.8 %

Procedure:
To a stirred solution of (5-{4-[(1R,2S)-2-(2,2-Dichloro-acetylamino)-3-fluoro-1-hydroxy-propyl]-phenyl}-oxazol-2-ylmethyl)-carbamic acid tert-butyl ester (0.006 g, 0.012 mmol) in CH2Cl2 (1.0 mL) is added trifluoroacetic acid (0.1 mL) at 0° C. and stirred at room temperature for 2 hours. Reaction mixture is concentrated in vacuum and the residue is washed with n-pentane dried under vacuum to give the title compound (0.005 g). 1H-NMR (400 MHz, DMSO-d6) δ: 4.22-4.28 (m, 1.5H), 4.31 (s, 2H), 4.40-4.44 (m, 0.5H), 4.56-4.60 (m, 0.5H), 4.68-4.71 (m, 0.5H), 4.89 (m, 1H), 6.02 (d, J=4.28 Hz, 1H), 6.49 (s, 1H), 7.47 (d, J=8.16 Hz, 2H), 7.67 (d, J=8.2 Hz, 2H), 7.72 (s, 1H), 8.21 (bs, 3H), 8.60 (d, J=8.88 Hz, 1H). LC-MS (m/z): [M+H]=376.1.
Reaction SMILES: CO[C:3](=O)[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10]/[CH:11]=[CH:12]\CCCCCCCC.C=C>[Ru]>[CH2:3]=[CH:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]
Reactant: CCCCCCCC/C=C\CCCCCCCC(=O)OC
Agent: [Ru]
Agent: C=C
Product: C=CCCCCCCCC
Reaction time: 20 h
Yield: 44.6 %

Procedure:
The supported ruthenium catalyst was evaluated in the metathesis of methyloleate with ethylene, in the manner described in Example 1, with the exception that the polymer-supported catalyst was weighed into the reactor first and swollen with 1 g of anhydrous, degassed toluene. A quantity of polymer-supported catalyst was used that correlated to a mole ratio of methyloleate to ruthenium of 4,500/1. Ethylene pressure was 60 psig (414 kPa); temperature was 50° C. Under these conditions, the supported catalyst achieved at 20 h a 1-decene yield of 44.6 percent, and a methyl-9-decenoate yield of 43.4 percent. The results indicate that the chelated ruthenium complex can be supported on a catalyst support and used as a heterogeneous catalyst in the olefin metathesis process of this invention.
Reaction SMILES: C(N=S(C1C=CC(CN)=CC=1)(C)=O)#N.[C:15]([N:17]=[S:18]([C:23]1[CH:40]=[CH:39][C:26]([CH2:27][N:28]2C(=O)C3C(=CC=CC=3)C2=O)=[CH:25][CH:24]=1)([CH:20]([CH3:22])[CH3:21])=[O:19])#[N:16]>>[C:15]([N:17]=[S:18]([C:23]1[CH:24]=[CH:25][C:26]([CH2:27][NH2:28])=[CH:39][CH:40]=1)([CH:20]([CH3:22])[CH3:21])=[O:19])#[N:16]
Reactant: CC(C)S(=O)(=NC#N)c1ccc(CN2C(=O)c3ccccc3C2=O)cc1
Agent: CS(=O)(=NC#N)c1ccc(CN)cc1
Product: CC(C)S(=O)(=NC#N)c1ccc(CN)cc1

Procedure:
The title compound is prepared in analogy to preparation 6d, substituting 2-(4-(N-cyano-S-methylsulfonimidoyl)benzyl)isoindoline-1,3-dione with 2-(4-(N-cyano-S-isopropylsulfonimidoyl)benzyl)isoindoline-1,3-dione (preparation 14b). ESI mass spectrum: [M+H]+=238; r.t. HPLC: 0.59 min (Z011_S03).
Reaction SMILES: [C:1]1(=[O:12])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4](=[O:11])[CH:3]=[CH:2]1.[CH2:13]([N:29]1[CH:33]=[CH:32][CH:31]=[CH:30]1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]>C(O)(=O)C>[CH2:13]([N:29]1[C:30]([C:3]2[C:4](=[O:11])[C:5]3[C:10]([C:1](=[O:12])[CH:2]=2)=[CH:9][CH:8]=[CH:7][CH:6]=3)=[CH:31][CH:32]=[C:33]1[C:3]1[C:4](=[O:11])[C:5]2[C:10]([C:1](=[O:12])[CH:2]=1)=[CH:9][CH:8]=[CH:7][CH:6]=2)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]
Reactant: CCCCCCCCCCCCCCCCn1cccc1
Reactant: O=C1C=CC(=O)c2ccccc21
Solvent: CC(=O)O
Product: CCCCCCCCCCCCCCCCn1c(C2=CC(=O)c3ccccc3C2=O)ccc1C1=CC(=O)c2ccccc2C1=O
Yield: 38 %

Procedure:
The same procedure as in Example 7 was followed by stirring 10 millimol of 1,4-naphthoquinone with 2.5 millimol of N-hexadecylpyrrole in 40 ml of acetic acid at 50° C. for 5 hours. The 1-hexadecyl-2,5-bis(1,4-naphthoquinon-2-yl)pyrrole was thus obtained in a yield of 38% after chromatography on a column of silica.
Reaction SMILES: [CH3:1][N:2]([CH3:13])[C:3]1[CH:8]=[CH:7][C:6]([NH2:9])=[C:5]([N+:10]([O-])=O)[CH:4]=1>[Pd]>[CH3:1][N:2]([CH3:13])[C:3]1[CH:4]=[C:5]([NH2:10])[C:6]([NH2:9])=[CH:7][CH:8]=1
Reactant: CN(C)c1ccc(N)c([N+](=O)[O-])c1
Agent: [Pd]
Product: CN(C)c1ccc(N)c(N)c1

Procedure:
In a 20 ml single-necked flask, introduce successively, under an argon atmosphere, 23 mg of N4,N4-dimethylbenzene-1,2,4-triamine, which can be obtained by catalytic hydrogenation of N4,N4-dimethyl-2-nitrobenzene-1,4-diamine in the presence of 10% palladium-on-charcoal under an initial hydrogen pressure of 5 bar at 20° C., 53 mg of (4-formyl-9H -fluoren-9(R,S)-yl)amide of 1H-pyrrolo[2,3-b]pyridine-4-carboxylic acid, prepared as in stage 6 of Example 234, and 24 mg of ferric chloride and 2 ml of dimethylformamide. After stirring for 3 h at 20° C., concentrate the solution under reduced pressure, and then take up the residue obtained in 4 ml of water. After draining of the insoluble material formed on a porous plate, washing with 2 ml of ethyl acetate and air-drying, in this way we obtain 41 mg of [4-(6-dimethylamino-1H-benzimidazol-2-yl)-9H-fluoren-9(R,S)-yl]amide of 1H-pyrrolo[2,3-b]-pyridine-4-carboxylic acid, in the form of a violet powder with the following characteristics:
Reaction SMILES: Cl[C:2]1[NH:3][C:4]2[CH:10]=[C:9]([Cl:11])[C:8]([C:12]([F:15])([F:14])[F:13])=[CH:7][C:5]=2[N:6]=1.Cl.[Cl:17][C:18]1[C:19]([N:24]2[CH2:29][CH2:28][NH:27][CH2:26][CH2:25]2)=[N:20][CH:21]=[CH:22][CH:23]=1>>[Cl:11][C:9]1[C:8]([C:12]([F:15])([F:14])[F:13])=[CH:7][C:5]2[NH:6][C:2]([N:27]3[CH2:28][CH2:29][N:24]([C:19]4[C:18]([Cl:17])=[CH:23][CH:22]=[CH:21][N:20]=4)[CH2:25][CH2:26]3)=[N:3][C:4]=2[CH:10]=1
Reactant: FC(F)(F)c1cc2nc(Cl)[nH]c2cc1Cl
Reactant: Clc1cccnc1N1CCNCC1
Agent: Cl
Product: FC(F)(F)c1cc2[nH]c(N3CCN(c4ncccc4Cl)CC3)nc2cc1Cl

Procedure:
2,5-Dichloro-6-(trifluoromethyl)benzoimidazole (255 mg, 1.0 mmol, Example 84c) reacted with 1-(3-chloropyridin-2-yl)piperazine hydrochloride (233 mg, 1.0 mmol, Example 3b) under the conditions of Example 3c to give the title compound as a white solid. M.p. 208.9-211.0° C. MS (ESI, pos. ion) m/z: 416.3, 420.1 (M+1).
Reaction SMILES: N1CCCCC1.[CH3:7][O:8][C:9](=[O:35])[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH2:16][NH:17]C(OCC2C3C=CC=CC=3C3C2=CC=CC=3)=O)[CH:11]=1.O.Cl>CN(C=O)C>[CH3:7][O:8][C:9](=[O:35])[C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH2:16][NH2:17])[CH:11]=1
Reactant: COC(=O)c1cccc(CNC(=O)OCC2c3ccccc3-c3ccccc32)c1
Agent: Cl
Solvent: C1CCNCC1
Solvent: CN(C)C=O
Solvent: O
Product: COC(=O)c1cccc(CN)c1
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
A 20% solution of piperidine in DMF (5 ml) was added to 3-[(9H-Fluoren-9-ylmethoxycarbonylamino)-methyl]-benzoic acid methyl ester (193 mg, 0.5 mmol) and the reaction was stirred at room temperature for 30 min. Water (10 ml) was added to the crude reaction mixture, followed by 1M HCl (10 ml). The aqueous layer was washed with EtOAc (3×10 ml) then basified to pH 9 with saturated NaHCO3. The basic layer was extracted with EtOAc (3×10 ml) and the aqueous layer was evaporated down to a small volume, then further extracted with EtOAc (5×10 ml). The combined organic layers were dried (MgSO4), filtered and the solvent evaporated in vacuo to give the title compound.
Reaction SMILES: [C:1]([C:4]1[CH:5]=[CH:6][C:7]([O:28][CH2:29][C:30]2[CH:35]=[C:34]([CH2:36][CH3:37])[CH:33]=[CH:32][N:31]=2)=[C:8]([C:10]2[CH:27]=[CH:26][C:13]3[CH2:14][CH2:15][N:16](C(OC(C)(C)C)=O)[CH2:17][CH2:18][C:12]=3[CH:11]=2)[CH:9]=1)(=[O:3])[CH3:2].C(O)(C(F)(F)F)=O>C(Cl)Cl>[CH2:36]([C:34]1[CH:33]=[CH:32][N:31]=[C:30]([CH2:29][O:28][C:7]2[CH:6]=[CH:5][C:4]([C:1](=[O:3])[CH3:2])=[CH:9][C:8]=2[C:10]2[CH:27]=[CH:26][C:13]3[CH2:14][CH2:15][NH:16][CH2:17][CH2:18][C:12]=3[CH:11]=2)[CH:35]=1)[CH3:37]
Reactant: CCc1ccnc(COc2ccc(C(C)=O)cc2-c2ccc3c(c2)CCN(C(=O)OC(C)(C)C)CC3)c1
Solvent: ClCCl
Solvent: O=C(O)C(F)(F)F
Product: CCc1ccnc(COc2ccc(C(C)=O)cc2-c2ccc3c(c2)CCNCC3)c1
Temperature: 25 °C

Procedure:
To a solution of 1,1-dimethylethyl 7-(5-acetyl-2-{[(4-ethyl-2-pyridinyl)methyl]oxy}phenyl)-1,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxylate, (0.217 g) in DCM (3 ml) was added TFA (0.4 ml). This was stirred at room temperature. After completion of reaction by tlc, the reaction mixture was concentrated in vacuo and purified by preparative hplc. Product fractions were concentrated in vacuo and the product obtained was partitioned between DCM and aqueous sodium bicarbonate. The organics were dried over sodium sulphate and concentrated in vacuo to yield the title compound, 0.035 g