Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: C[O:2][C:3](=[O:22])[C@@H:4]([N:7]1[CH2:11][C:10]([O:12][C:13]2[C:18]([F:19])=[CH:17][CH:16]=[CH:15][C:14]=2[F:20])=[CH:9][C:8]1=[O:21])[CH2:5][CH3:6].O.[OH-].[Li+].O>O1CCCC1.O>[F:20][C:14]1[CH:15]=[CH:16][CH:17]=[C:18]([F:19])[C:13]=1[O:12][C:10]1[CH2:11][N:7]([C@@H:4]([CH2:5][CH3:6])[C:3]([OH:22])=[O:2])[C:8](=[O:21])[CH:9]=1
Reactant: CC[C@@H](C(=O)OC)N1CC(Oc2c(F)cccc2F)=CC1=O
Agent: [Li+]
Agent: [OH-]
Solvent: C1CCOC1
Solvent: O
Product: CC[C@@H](C(=O)O)N1CC(Oc2c(F)cccc2F)=CC1=O
Temperature: 25 °C
Reaction time: 2 h
Yield: 0.1 %

Procedure:
To a solution of (S)-2-[4-(2,6-difluoro-phenoxy)-2-oxo-2,5-dihydro-pyrrol-1-yl]-butyric acid methyl ester (0.119 g, 0.38 mol) in tetrahydrofuran:water (1:1, 8 mL) was added lithium hydroxide monohydrate (0.050 g 1.19 mmol). The mixture was stirred at room temperature for 2 h. The reaction mixture was poured into water and washed with diethyl ether and the ether layer discarded. The aqueous phase was acidified with 1N aqueous hydrochloric acid (pH <2), and extracted with ethyl acetate (2×30 mL). The combined ethyl acetate layers were dried over magnesium sulfate, filtered and concentrated to afford (S)-2-[4-(2,6-difluoro-phenoxy)-2-oxo-2,5-dihydro-pyrrol-1-yl]-butyric acid (0.090 g, 83%) as an off-white solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 0.87 (t, J=7.4 Hz, 3H), 1.60-2.06 (m, 2H), 4.23 (d, J=18.7 Hz, 1H), 4.31 (d, J=18.7 Hz, 1H), 4.43 (dd, J=10.7, 5.0 Hz, 1H), 5.05 (s, 1H), 7.21-7.54 (m, 3H), 12.94 (br. s., 1H).
Reaction SMILES: [CH2:1]([NH:8][C:9]([NH:13][C:14]1[CH:19]=[CH:18][C:17]([C@H:20]([C:28]2[CH:33]=[CH:32][C:31]([O:34][CH:35]([F:37])[F:36])=[C:30]([O:38][CH:39]([F:41])[F:40])[CH:29]=2)[CH2:21][C:22]2[CH:27]=[CH:26][N:25]=[CH:24][CH:23]=2)=[CH:16][CH:15]=1)=[N:10][C:11]#[N:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClC1C=CC=C(C(OO)=[O:50])C=1>>[CH2:1]([NH:8][C:9]([NH:13][C:14]1[CH:19]=[CH:18][C:17]([C@H:20]([C:28]2[CH:33]=[CH:32][C:31]([O:34][CH:35]([F:36])[F:37])=[C:30]([O:38][CH:39]([F:41])[F:40])[CH:29]=2)[CH2:21][C:22]2[CH:23]=[CH:24][N+:25]([O-:50])=[CH:26][CH:27]=2)=[CH:16][CH:15]=1)=[N:10][C:11]#[N:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: O=C(OO)c1cccc(Cl)c1
Reactant: N#CN=C(NCc1ccccc1)Nc1ccc([C@@H](Cc2ccncc2)c2ccc(OC(F)F)c(OC(F)F)c2)cc1
Product: N#CN=C(NCc1ccccc1)Nc1ccc([C@@H](Cc2cc[n+]([O-])cc2)c2ccc(OC(F)F)c(OC(F)F)c2)cc1

Procedure:
From the compound of Example 11 (340 mg, 0.62 mmol) and 50% m-chloroperbenzoic acid as a white solid (200 mg). 1Hnmr (300 MHz, CDCl3) δ 3.27 (2H, d, J 8.0 Hz), 4.14 (1H, t, J 7.86 Hz), 4.48 (2H, d, J 5.72 Hz), 5.29 (1H, br), 6.48 (2H, t, J 73.49 Hz), 6.85 (2H, d, J 7.02 Hz), 7.00 (1H, dd, J 2.19, 8.43 Hz), 7.06 (1H, br), 7.12-7.34 (1OH, c), 7.50 (1H, br) and 7.98 (2H, d, J 7.03 Hz). m/z (ESI, 60V) 580 (MH+, 85), 538 (100), 429 (41).
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4]([C@@H:8]2[C@@H:13]([C:14]3[CH:19]=[CH:18][C:17]([Cl:20])=[CH:16][CH:15]=3)[N:12]([C@@H:21]([CH2:26][CH3:27])[CH:22]=[CH:23][C:24]#[N:25])[C:11](=[O:28])[C@:10]([CH2:30][CH:31]3[CH2:35][O:34][C:33]([CH3:37])([CH3:36])[O:32]3)([CH3:29])[CH2:9]2)[CH:5]=[CH:6][CH:7]=1.[H][H]>CCO.[Pd]>[Cl:1][C:2]1[CH:3]=[C:4]([C@@H:8]2[C@@H:13]([C:14]3[CH:15]=[CH:16][C:17]([Cl:20])=[CH:18][CH:19]=3)[N:12]([C@@H:21]([CH2:26][CH3:27])[CH2:22][CH2:23][C:24]#[N:25])[C:11](=[O:28])[C@:10]([CH2:30][CH:31]3[CH2:35][O:34][C:33]([CH3:36])([CH3:37])[O:32]3)([CH3:29])[CH2:9]2)[CH:5]=[CH:6][CH:7]=1
Reactant: CC[C@@H](C=CC#N)N1C(=O)[C@@](C)(CC2COC(C)(C)O2)C[C@H](c2cccc(Cl)c2)[C@H]1c1ccc(Cl)cc1
Reactant: [H][H]
Agent: [Pd]
Solvent: CCO
Product: CC[C@@H](CCC#N)N1C(=O)[C@@](C)(CC2COC(C)(C)O2)C[C@H](c2cccc(Cl)c2)[C@H]1c1ccc(Cl)cc1
Temperature: 25 °C
Reaction time: 1.5 h

Procedure:
To a solution of (4S)-4-((3R,5R,6S)-5-(3-chlorophenyl)-6-(4-chlorophenyl)-3-((2,2-dimethyl-1,3-dioxolan-4-yl)methyl)-3-methyl-2-oxopiperidin-1-yl)hex-2-enenitrile prepared above in Step E (208 mg, 0.384 mmol) in EtOH (12.8 mL) was added 10% palladium on activated carbon (40.9 mg, 0.038 mmol). Then the reaction mixture was subjected to regular hydrogenation with hydrogen (0.774 mg, 0.384 mmol). After being stirred at rt for 1.5 h, the catalyst was filtered using a short plug of silica-gel and washed (EtOAc). The combined organic solutions were concentrated under reduced pressure. Purification by combi flash (flash column chromatography, Teledyne Isco, Lincoln, Nebr.) (SiO2, 24 g, 35% and 40% EtOAc/Hexanes) provided the title compound as a colorless film.
Reaction SMILES: [O:1]=[CH:2][C@@H:3]([C@H:5]([C@@H:7]([C@@H:9]([CH2:11][OH:12])[OH:10])[OH:8])[OH:6])[OH:4].[CH2:13]([OH:35])[C@H:14]1[O:19][C@@H:18]([O:20][C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H:17]([OH:32])[C@@H:16]([OH:33])[C@@H:15]1[OH:34]>>[OH:12][CH2:11][C@@H:9]([C@H:7]([C@@H:5]([C@@H:3]([CH2:2][OH:1])[OH:4])[OH:6])[OH:8])[OH:10].[CH2:18]([OH:20])[C@H:17]([C@H:16]([C@@H:15]([C@@H:14]([CH2:13][OH:35])[OH:19])[OH:34])[OH:33])[OH:32]
Reactant: OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O
Reactant: O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO
Product: OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)CO
Product: OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO

Procedure:
The yield for the C6 compounds (sorbitol, mannitol and glucose) was calculated relative to the concentration of glucose and cellobiose in the reaction solution prior to the reaction. The C6 sugar alcohol yield (sorbitol, mannitol) was 84.0%, the glucose yield was 13.4%. The yield for xylitol (84.2%) and xylose (11.7%) were calculated relative to the concentration of xylose in the reaction solution prior to the reaction. Furthermore, glycerol, 1,3-propanediol, methanol, levulinic acid, hydroxymethylfurfural and furfural and furan acid were identified as by-products.
Reaction SMILES: [CH3:1][C:2]([CH2:9][CH2:10][CH:11]=[C:12]([CH3:18])[CH2:13][O:14][CH2:15][O:16][CH3:17])=[CH:3][CH2:4][CH2:5][C:6](=[O:8])[CH3:7].[Cl-].[NH4+].O1CC[CH2:23][CH2:22]1>>[CH3:7][C:6]([OH:8])([CH2:5][CH2:4][CH:3]=[C:2]([CH3:1])[CH2:9][CH2:10][CH:11]=[C:12]([CH3:18])[CH2:13][O:14][CH2:15][O:16][CH3:17])[C:22]#[CH:23]
Reactant: COCOCC(C)=CCCC(C)=CCCC(C)=O
Reactant: C1CCOC1
Agent: [Cl-]
Agent: [NH4+]
Product: C#CC(C)(O)CCC=C(C)CCC=C(C)COCOC
Temperature: 25 °C
Reaction time: 3 h
Yield: 83 %

Procedure:
A solution of 6,10-dimethyl-11-(methoxymethyl)oxy-5,9-undecadien-2-one (67 mg, 0.26 mmol) in tetrahydrofuran (2 ml) was stirred on an ice bath under argon atmosphere. To the solution was added lithium acetylide ethylenediamine complex (30 mg, 0.33 mmol), and the mixture was warmed to room temperature and stirred for 3 hours. After addition of saturated aqueous ammonium chloride (2 ml), the reaction mixture was extracted with ether. The extract was dried over Na2SO4 and evaporated in vacuo to remove the solvent to give a crude product, which was purified with silica gel column chromatography to obtain 3,7,11-trimethyl-12-(methoxymethyl)oxy-6,10-dodecadien-1-in-3-ol (61 mg, 83%).
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[C:4]([C:9]#[C:10][C:11]([C:13]2[CH:14]=[N:15][C:16]3[C:21]([CH:22]=2)=[CH:20][CH:19]=[CH:18][CH:17]=3)=O)[CH:5]=[C:6]([Cl:8])[CH:7]=1.Cl.[NH:24]([C@H:26]([C:28]1[CH:38]=[CH:37][C:31]([C:32]([O:34][CH2:35][CH3:36])=[O:33])=[CH:30][CH:29]=1)[CH3:27])[NH2:25].C(N(CC)CC)C>CN(C=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[CH:10]=[C:11]([C:13]3[CH:14]=[N:15][C:16]4[C:21]([CH:22]=3)=[CH:20][CH:19]=[CH:18][CH:17]=4)[N:24]([C@H:26]([C:28]3[CH:38]=[CH:37][C:31]([C:32]([O:34][CH2:35][CH3:36])=[O:33])=[CH:30][CH:29]=3)[CH3:27])[N:25]=2)[CH:5]=[C:6]([Cl:8])[CH:7]=1
Reactant: O=C(C#Cc1cc(Cl)cc(Cl)c1)c1cnc2ccccc2c1
Reactant: CCOC(=O)c1ccc([C@H](C)NN)cc1
Agent: Cl
Solvent: CN(C)C=O
Solvent: CCN(CC)CC
Product: CCOC(=O)c1ccc([C@H](C)n2nc(-c3cc(Cl)cc(Cl)c3)cc2-c2cnc3ccccc3c2)cc1

Procedure:
To a solution of the intermediate from step C (152 mg, 0.46 mmol) in DMF (5 mL) was added the ethyl 4-[(1S)-1-hydrazinoethyl]benzoate hydrochloride (126 mg, 0.51 mmol) and triethyl amine (86 μL, 0.61 mmol). After stirring, the reaction mixture at room temperature for 2 hours it was concentrated in vacuo. The residue was diluted with water and ethyl acetate. The organic layer was washed with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by flash chromatography using 10% ethyl acetate-hexanes. This material was then re-purified with 75% hexanes-dichloromethane to give the desired compound as the major product. 1H NMR (CDCl3, 500 MHz): 8.84 (d, J=2.0 Hz, 1H), 8.18 (d, J=8.5 Hz, 1H), 8.03 (d, J=8.2 Hz, 2H), 7.99 (d, J=2.1 Hz, 1H), 7.83 (d, J=1.8 Hz, 2H), 7.78 (m, 1H), 7.62 (t, J=8.0 Hz, 1H), 7.34 (t, J=1.8 Hz, 1H), 7.28 (d, J=8.2 Hz, 2H), 6.77 (s, 1H), 5.58 (q, J=7.1 Hz, 1H), 4.41 (q, J=7.1 Hz, 2H), 2.02 (d, J=7.1 Hz, 3H), 1.4 (t, J=7.0 Hz, 3H). LC-MS: 4.64 min; (M+H)=516.3.
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:22]=[CH:21][C:6]([CH2:7][N:8]2[C:12]3[N:13]=[CH:14][C:15]4[CH2:16][NH:17][CH2:18][CH2:19][C:20]=4[C:11]=3[CH:10]=[N:9]2)=[CH:5][CH:4]=1.C(N(CC)CC)C.[Cl:30][CH:31]([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C:32](Cl)=[O:33]>ClCCl>[Cl:30][CH:31]([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C:32]([N:17]1[CH2:16][C:15]2[CH:14]=[N:13][C:12]3[N:8]([CH2:7][C:6]4[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:22][CH:21]=4)[N:9]=[CH:10][C:11]=3[C:20]=2[CH2:19][CH2:18]1)=[O:33]
Reactant: COc1ccc(Cn2ncc3c4c(cnc32)CNCC4)cc1
Reactant: O=C(Cl)C(Cl)c1ccccc1
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: COc1ccc(Cn2ncc3c4c(cnc32)CN(C(=O)C(Cl)c2ccccc2)CC4)cc1
Temperature: 25 °C
Reaction time: 1 h
Yield: 85.3 %

Procedure:
To a solution of 3-(4-methoxybenzyl)-6,7,8,9-tetrahydro-3H-pyrazolo[3,4-c][2,7]naphthyridine (1.536 g, 5.22 mmol) in anhydrous dichloromethane (20 mL) was added triethylamine (2.18 mL, 15.66 mmol) followed by 2-chloro-2-phenylacetyl chloride (90%, 1.05 mL, 6.52 mmol). The mixture was stirred at room temperature for 1 hour. The reaction was quenched by the addition of water (10 mL). The reaction mixture was extracted with dichloromethane (10 mL) and the organic layer washed with brine (2×10 mL), dried (Na2SO4), filtered and concentrated under reduced pressure to give the crude product. The crude product was purified by flash column chromatography (SiO2, gradient from 40% EtOAc in hexanes to 50% EtOAc in hexanes) to give the desired product, 2-chloro-1-(3-(4-methoxybenzyl)-8,9-dihydro-3H-pyrazolo[3,4-c][2,7]naphthyridin-7(6H)-yl)-2-phenylethanone as an off-white solid (1.99 g, 85%). 1H NMR (400 MHz, DMSO-d6) δ 8.43/8.24 (s, 1H, rotamers), 8.15/8.12 (s, 1H, rotamers), 7.52 (m, 2H), 7.40 (m, 3H), 7.17 (m, 2H), 6.83 (m, 2H), 6.53/6.48 (s, 1H, rotamers), 5.56 (s, 2H), 5.02-4.70 (m, 2H), 3.84 (m, 2H), 3.68 (s, 3H), 3.11/2.67 (m, 2H, rotamers); LCMS [M+H]: 447.
Reaction SMILES: Cl.Cl[CH2:3][C:4]1[CH:13]=[CH:12][C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[N:5]=1.[NH:14]1[CH:18]=[CH:17][N:16]=[CH:15]1.C(=O)([O-])[O-].[Na+].[Na+]>CN(C)C=O>[N:14]1([CH2:3][C:4]2[CH:13]=[CH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[N:5]=2)[CH:18]=[CH:17][N:16]=[CH:15]1
Reactant: ClCc1ccc2ccccc2n1
Reactant: c1c[nH]cn1
Agent: Cl
Agent: O=C([O-])[O-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: c1ccc2nc(Cn3ccnc3)ccc2c1
Yield: 21.5 %

Procedure:
A mixture consisting of 2-chloromethylquinoline hydrochloride (10.0 g.), imidazole (3.2 g.) and sodium carbonate (14.8 g.) in N,N-dimethylformamide (100 ml.) was heated on a steam bath for a period of seven hours and then evaporated. The residue was taken up in chloroform and the resulting solution was filtered to give a clear filtrate. Evaporation of the latter liquid while under reduced pressure then gave a solid substance, which was subsequently crystallized from chloroform/petroleum ether (b.p. 60°-80° C.) and then recrystallized from diethyl ether to give pure 2-(1-imidazol-1-ylmethyl)quinoline (yield, 2.10 g.), m.p. 106°-107° C.
Reaction SMILES: Br[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:10]=1[NH:9][CH:8]=[CH:7]2.[C:11]1(B(O)O)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C(=O)([O-])[O-].[K+].[K+].ClCCl>O1CCOCC1.O>[C:11]1([C:2]2[CH:3]=[CH:4][CH:5]=[C:6]3[C:10]=2[NH:9][CH:8]=[CH:7]3)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1
Reactant: OB(O)c1ccccc1
Reactant: Brc1cccc2cc[nH]c12
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: ClCCl
Solvent: O
Solvent: C1COCCO1
Product: c1ccc(-c2cccc3cc[nH]c23)cc1
Temperature: 100 °C
Yield: 93.1 %

Procedure:
To a suspension of 7-bromo-1H-indole (196 mg, 0.00100 mol) in 1,4-dioxane (4 mL) and water (1 mL) was added phenylboronic acid (146 mg, 0.00120 mol), potassium carbonate (414 mg, 0.00300 mol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II),complex with dichloromethane (1:1) (82 mg, 0.00010 mol). The flask was evacuated and refilled with nitrogen, three times then the mixture was heated at 100° C. overnight. The mixture was diluted with EtOAc (30 mL), washed with sat. aq. NaHCO3 (10 mL) and brine (10 mL), then dried over anhydrous sodium sulfate and the solvent removed in vacuo. The crude material was purified by chromatography over silica gel eluting with hexane/EtOAc to give the title compound (180 mg, 93% yield). 1H NMR (CDCl3, 400 MHz): δ 6.64 (dd, J=3.0, 2.0 Hz, 1H), 7.18-7.26 (m, 3H), 7.41 (t, J=7.5 Hz, 1H), 7.48-7.57 (m, 2H), 7.61-7.70 (m, 3H) and 8.43 (br s, 1H) ppm. LC-MS (ES+.): 194 [MH+].
Reaction SMILES: [Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[N:9]1[C:13]([CH2:14]O)=[C:12]([CH:16]([CH3:18])[CH3:17])[N:11]=[N:10]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cl:38]CCl>C(Cl)(Cl)(Cl)Cl>[Cl:38][CH2:14][C:13]1[N:9]([C:3]2[C:2]([Cl:1])=[CH:7][CH:6]=[CH:5][C:4]=2[Cl:8])[N:10]=[N:11][C:12]=1[CH:16]([CH3:18])[CH3:17]
Reactant: CC(C)c1nnn(-c2c(Cl)cccc2Cl)c1CO
Reactant: ClCCl
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: ClC(Cl)(Cl)Cl
Product: CC(C)c1nnn(-c2c(Cl)cccc2Cl)c1CCl
Yield: 86 %

Procedure:
To a solution of [3-(2,6-dichloro-phenyl)-5-isopropyl-3H-[1,2,3]triazol-4-yl]-methanol (0.100 g) in dichloromethane (2 mL) and carbon tetrachloride (2 mL) is added triphenyl phosphine (0.275 g). Upon completion, the reaction is concentrated under reduced pressure. The residue is dissolved in dichloromethane to aid in loading solubility and is purified via filter chromatography eluting with 10% ethyl acetate in toluene to give the desired product (0.091 g, 86%). 1H NMR (400 MHz, CDCl3) δ 7.58-7.54 (d, 2H), 7.52-7.50 (t, 1H), 4.48 (s, 2H), 3.24-3.21 (m, 1H), 1.51-1.49 (d, 6H).
Reaction SMILES: [OH:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[N:9]1[N:13]=[C:12]2[CH:14]=[CH:15][C:16]([O:18][C:19]([CH2:22][C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:21])[CH3:20])=[CH:17][C:11]2=[N:10]1.N(C(C)(C)C#N)=NC(C)(C)C#N.[Br:39]Br>C(Cl)(Cl)(Cl)Cl>[OH:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][Br:39])=[CH:4][C:3]=1[N:9]1[N:13]=[C:12]2[CH:14]=[CH:15][C:16]([O:18][C:19]([CH2:22][C:23]([CH3:26])([CH3:25])[CH3:24])([CH3:21])[CH3:20])=[CH:17][C:11]2=[N:10]1
Reactant: Cc1ccc(O)c(-n2nc3ccc(OC(C)(C)CC(C)(C)C)cc3n2)c1
Reactant: BrBr
Agent: CC(C)(C#N)N=NC(C)(C)C#N
Solvent: ClC(Cl)(Cl)Cl
Product: CC(C)(C)CC(C)(C)Oc1ccc2nn(-c3cc(CBr)ccc3O)nc2c1
Temperature: 25 °C

Procedure:
2-(2′-hydroxy-5′-bromomethyphenyl)-5-tert-octyloxybenzotriazole was prepared from the bromination of 2-(2′-hydroxy-5′-methyphenyl)-5-tert-octyloxybenzotriazole using azobis isobutyronitrile (AIBN) as an initiator. In a 500 ml three-necked round bottomed flask 8.236 g (0.0223 mol) 2-(2′-hydroxy-5′-methyphenyl)-5-tert-octyloxy benzotriazole and 100 mg of AIBN were taken and dissolved in 150 ml of dry carbon tetrachloride. In a separate conical flask 4.18 g (1.5 ml, 0.03 mol) of bromine was dissolved in 75 ml of dry carbon tetrachloride and solution was transferred to a cylindrical funnel with pressure equalizing tube. Three-necked round-bottomed flask containing solution of 2-(2′-hydroxy-5′-methyphenyl)-5-tert-octyloxybenzotriazole was kept in oil-bath with temperature 50° C. Nitrogen was bubbled through the solution for creating inert atmosphere. Cylindrical funnel containing bromine solution was mounted on the three-necked round-bottomed flask. Solution in the flask was continuously stirred with the help of magnetic stirrer. Bromine solution was added, drop-by-drop, from funnel to the flask for a span of 4-5 hours till all the solution was poured out. After that heating was stopped and the final reaction mixture was allowed to cool at room temperature. Product was separated by solvent evaporation. Finally the product was purified by recrystallization from acetone. The yield of 2-(2′-hydroxy-5′-bromomethyphenyl)-5-tert-octyloxybenzotriazole was 7.8 g (81%).
Reaction SMILES: [CH2:1]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[NH:15][C:16](=[O:30])[NH:17][C:18]1[CH:23]=[CH:22][C:21]([CH2:24][C:25]([OH:27])=O)=[CH:20][C:19]=1[O:28][CH3:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH:31]1[CH2:35][CH2:34][CH2:33][CH:32]1[CH2:36][O:37][C:38]1[CH:47]=[CH:46][C:41]([C:42]([O:44][CH3:45])=[O:43])=[CH:40][C:39]=1[N+:48]([O-:50])=[O:49].C1C=CC2N(O)N=[N:57]C=2C=1.CCN=C=NCCCN(C)C.Cl>CN(C1C=CN=CC=1)C.C1COCC1.O>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[NH:15][C:16](=[O:30])[NH:17][C:18]1[CH:23]=[CH:22][C:21]([CH2:24][C:25]([NH:57][N:31]2[CH2:35][CH2:34][CH2:33][CH:32]2[CH2:36][O:37][C:38]2[CH:47]=[CH:46][C:41]([C:42]([O:44][CH3:45])=[O:43])=[CH:40][C:39]=2[N+:48]([O-:50])=[O:49])=[O:27])=[CH:20][C:19]=1[O:28][CH3:29])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: COc1cc(CC(=O)O)ccc1NC(=O)Nc1ccccc1OCc1ccccc1
Reactant: COC(=O)c1ccc(OCC2CCCN2)c([N+](=O)[O-])c1
Reactant: On1nnc2ccccc21
Agent: CCN=C=NCCCN(C)C
Agent: CN(C)c1ccncc1
Agent: Cl
Solvent: C1CCOC1
Solvent: O
Product: COC(=O)c1ccc(OCC2CCCN2NC(=O)Cc2ccc(NC(=O)Nc3ccccc3OCc3ccccc3)c(OC)c2)c([N+](=O)[O-])c1
Temperature: 25 °C
Reaction time: 12 h
Yield: 404.2 %

Procedure:
To a solution of 4-[N′-(2-benzyloxyphenyl)ureido]-3-methoxyphenylacetic acid (1.12 g, 2.76 mmol), methyl 4-(2-pyrrolidinylmethoxy)-3-nitrobenzoate (890 mg, 2.76 mmol), HOBt (74.0 mg, 0.55 mmol), DMAP (67.0 mg, 0.55 mmol), and Et3 N (0.58 mL, 4.13 mmol) in THF (15 mL) was added EDC.HCl (792 mg, 4.13 mmol). After being stirred at room temperature for 12 hr, the reaction mixture was diluted with water and extracted with EtOAc. The extracts were washed with brine, dried over Na2SO4, and concentrated to dryness. Chromatography of the residue with EtOAc as eluent gave methyl 4-[1-[4-[N′-(2-benzyloxyphenyl)ureido]-3-methoxyphenylacetamido ]-2-pyrrolidinylmethoxy]-3-nitrobenzoate (1.52 g, 82%) as a yellow amorphous solid. 1H-NMR (CDCl3) δ 1.91 (m, 1H), 1.95–2.17 (m, 3H), 3.47–3.53 (m, 2H), 3.56 (s, 2H), 3.60 (m, 1H), 3.68 (s, 3H), 3.90 (s, 3H), 4.11 (d, J=7.3 Hz, 1 H), 4.45 (m, 1H), 5.08 (s, 2H), 6.70 (dd, J=8.3, 1.9 Hz, 1H), 6.75 (d, J=1.9 Hz, 1H), 6.91–6.99 (m, 31H), 7.16 (s, 1H), 7.18 (d, J=8.3 Hz, 1H), 7.33–7.40 (m, 6H), 7.91 (d, J=8.3 Hz, 1H), 8.11–8.16 (m, 2H), 8.46 (s, 1H).
Reaction SMILES: [CH3:1][C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[CH2:3].C([C:14](=[O:18])[C:15]([O-:17])=[O:16])CCC.C(=O)(O)[O-].[Na+].[C:24]1(C)[CH:29]=CC=[CH:26][CH:25]=1>>[OH:18][CH:14]([CH2:3][C:2]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[CH2:1])[C:15]([O:17][CH2:29][CH2:24][CH2:25][CH3:26])=[O:16]
Reactant: CCCCC(=O)C(=O)[O-]
Reactant: Cc1ccccc1
Reactant: C=C(C)c1ccccc1
Agent: O=C([O-])O
Agent: [Na+]
Product: C=C(CC(O)C(=O)OCCCC)c1ccccc1
Reaction time: 1 h
Yield: 82 %

Procedure:
To 118 mg (1 mmol) of α-methylstyrene and 130 mg (1 mmol) of n-butylglyoxylate was added at 0° C. the solution of the complex in toluene obtained in Example 1 (2). After stirring for 1 hour, the reaction mixture was poured into a saturated aqueous solution of sodium bicarbonate and filtered through celite. Then the filtrate was extracted with ether thrice and dried over anhydrous magnesium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography (hexane/ethyl acetate=15/1). Thus 213 mg of n-butyl 2-hydroxy-4-phenyl-4-pentenoate was obtained (yield: 82%). When measured with CHIRALPAK AS column (manufactured by Daicel Chemical Industries) [hexane:i-PrOH=3:1, flow rate: 0.5 ml/min], the optical purity of this product was 97.5% e.e.
Reaction SMILES: [F:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([O:12][CH3:13])=[C:4]([CH:14]=[O:15])[CH:3]=1.O.P([O-])(O)(O)=[O:18].[Na+].OO.Cl([O-])=O.[Na+]>C(#N)C.O>[F:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([O:12][CH3:13])=[C:4]([C:14]([OH:18])=[O:15])[CH:3]=1
Reactant: COc1c(C=O)cc(F)c2ccccc12
Reactant: O=P([O-])(O)O
Agent: OO
Agent: [Na+]
Agent: [O-][Cl+][O-]
Solvent: O
Solvent: CC#N
Product: COc1c(C(=O)O)cc(F)c2ccccc12
Reaction time: 2.5 h
Yield: 280.5 %

Procedure:
9.3 g of 4-fluoro-1-methoxynaphthalene-2-carbaldehyde were dissolved in 100 mL of acetonitrile. 2.1 g sodium dihydrogenphosphate monohydrate in 10 mL of water were added, followed by the addition of 9.5 mL hydrogen peroxide (30%). 8.9 g sodium chlorite, dissolved in 20 mL water were added dropwise while maintaining an internal temperature between 5° C. and 15° C. The reaction was then allowed to come to room temp over 2.5 h. The precipitated solid was filtered with suction, and the solid was washed with water, and dried in vacuo at 40° C. to yield 9.4 g of 4-fluoro-1-methoxynaphthalene-2-carboxylic acid. The filtrate was treated with 60 mL of cold 10% aqueous sodium bisulfite solution. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and brine. The organic layer was washed with 0.2 N NaOH twice. The washes were acidified with 6 N HCl to pH 3, whereupon crystallization occurred. The precipitating product was filtered, washed with water and dried in vacuo at 40° C. to yield a second batch of 1.0 g of 4-fluoro-1-methoxynaphthalene-2-carboxylic acid.
Reaction SMILES: [CH2:1]([CH:7]1[CH2:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:16]3[CH:21]=[CH:20][C:19]([C:22](=O)[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:18][N:17]=3)[CH:13]=2)[CH2:8]1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6].C(O)COCCO.O.NN.[OH-].[K+]>C(OCC)(=O)C.O>[CH2:1]([CH:7]1[CH2:15][C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:16]3[CH:21]=[CH:20][C:19]([CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])=[CH:18][N:17]=3)[CH:13]=2)[CH2:8]1)[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6]
Reactant: CCCCCCCCCC(=O)c1ccc(-c2ccc3c(c2)CC(CCCCCC)C3)nc1
Agent: NN
Agent: [K+]
Agent: [OH-]
Solvent: OCCOCCO
Solvent: CCOC(C)=O
Solvent: O
Product: CCCCCCCCCCc1ccc(-c2ccc3c(c2)CC(CCCCCC)C3)nc1
Reaction time: 1 h
Yield: 37.2 %

Procedure:
0.50 g (1.15 mM) of 2-hexyl-5-(5-decanoylpyridine-2-yl) indan, 3.5 ml of diethylene glycol, 0.18 ml (2.96 mM) of 80%-hydrazine hydrate (density: 1.03), and 0.23 g (3.48 mM) of 85%-KOH were mixed and heat-stirred for 1 hour at 144°-216° C. After the reaction, the reaction mixture was poured into water, followed by addition of ethyl acetate and saturated common salt aqueous solution and stirring at room temperature to obtain an insoluble matter through filtration under reduced pressure. The insoluble matter was dissolved in toluene and dried with anhydrous sodium sulfate. The filtrate was subjected to extraction with ethyl acetate and washed with saturated common salt aqueous solution, followed by drying with anhydrous sodium sulfate. Each of the sodium sulfate was removed by filtration and each of the filtrate (toluene solution and ethyl acetate solution) was evaporated into a residue. The thus-prepared two-species of residues were mixed and purified by silica gel column chromatography (eluent: toluene), followed by concentration. To the concentrated matter, methanol was added, followed by cooling in a refrigerator. After the cooling, the resultant insoluble matter was recovered by filtration to obtain 0.18 g of 2-hexyl-5-(5-decylpyridine-2-yl)indan (Yield: 37.2%). ##STR306##