Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:7][C:8]([CH3:15])=[CH:9][C:10](OCC)=[O:11].F>>[CH3:7][C:8]1([CH3:15])[C:6]2[C:1](=[CH:2][CH:3]=[CH:4][CH:5]=2)[C:10](=[O:11])[CH2:9]1
Reactant: CCOC(=O)C=C(C)C
Reactant: c1ccccc1
Agent: F
Product: CC1(C)CC(=O)c2ccccc21
Temperature: 70 °C
Reaction time: 1 h
Yield: 96.7 %

Procedure:
7.81 g (100 mmol) of benzene and 14.4 g (112 mmol) of ethyl 3,3-dimethylacrylate were reacted analogously with 100 g (5 mol) of liquid hydrogen fluoride and the mixture was stirred at 70° C. for 1 hour. The work-up was carried out analogously to Example A, giving 15.5 g of the compound (3) in a purity of 96% (GC). (Yield: 93.1% of theory). 1H-NMR spectra (100 MHz, CDCl3): 3:7.77-7.25 (m,4H), 2.57 (s,2H), 1.37 (s,6H).
Reaction SMILES: [NH2:1][C@H:2]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[CH2:3][CH2:4][N:5]1[CH2:10][CH2:9][CH:8]([C:11]2[CH:12]=[C:13]([NH:17][C:18](=[O:22])[CH:19]([CH3:21])[CH3:20])[CH:14]=[CH:15][CH:16]=2)[CH2:7][CH2:6]1.[Cl:29][C:30]1[C:35]([C:36](Cl)=[O:37])=[CH:34][N:33]=[C:32]2[N:39]([CH3:43])[N:40]=[C:41]([CH3:42])[C:31]=12>>[Cl:29][C:30]1[C:35]([C:36]([NH:1][C@H:2]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[CH2:3][CH2:4][N:5]2[CH2:10][CH2:9][CH:8]([C:11]3[CH:16]=[CH:15][CH:14]=[C:13]([NH:17][C:18](=[O:22])[CH:19]([CH3:21])[CH3:20])[CH:12]=3)[CH2:7][CH2:6]2)=[O:37])=[CH:34][N:33]=[C:32]2[N:39]([CH3:43])[N:40]=[C:41]([CH3:42])[C:31]=12
Reactant: CC(C)C(=O)Nc1cccc(C2CCN(CC[C@H](N)c3ccccc3)CC2)c1
Reactant: Cc1nn(C)c2ncc(C(=O)Cl)c(Cl)c12
Product: Cc1nn(C)c2ncc(C(=O)N[C@@H](CCN3CCC(c4cccc(NC(=O)C(C)C)c4)CC3)c3ccccc3)c(Cl)c12

Procedure:
Prepared by Procedure Q1 and Scheme AC using N-(3-{1-((3S)-3-amino-3-phenylpropyl]-4-piperidinyl}phenyl)-2-methylpropanamide and 4-chloro-1,3-dimethyl-1H-pyrazolo[3,4-b]pyridine-5-carbonyl chloride: ESMS m/e: 587.3 (M+H)+.
Reaction SMILES: [OH:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9](=[O:23])[C:10]([CH3:22])([CH3:21])[O:11][C:12]=2[C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=2)=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CN(C=O)C.[Cl:35][C:36]1[CH:37]=[CH:38][C:39]2[N:40]([CH:42]=[C:43]([CH2:45]Cl)[N:44]=2)[CH:41]=1>O>[Cl:35][C:36]1[CH:37]=[CH:38][C:39]2[N:40]([CH:42]=[C:43]([CH2:45][O:1][C:2]3[CH:3]=[CH:4][C:5]([C:8]4[C:9](=[O:23])[C:10]([CH3:21])([CH3:22])[O:11][C:12]=4[C:13]4[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=4)=[CH:6][CH:7]=3)[N:44]=2)[CH:41]=1
Reactant: COc1ccc(C2=C(c3ccc(O)cc3)C(=O)C(C)(C)O2)cc1
Reactant: ClCc1cn2cc(Cl)ccc2n1
Agent: O=C([O-])[O-]
Agent: [Cs+]
Solvent: O
Solvent: CN(C)C=O
Product: COc1ccc(C2=C(c3ccc(OCc4cn5cc(Cl)ccc5n4)cc3)C(=O)C(C)(C)O2)cc1
Temperature: 80 °C
Yield: 39.5 %

Procedure:
4-(4-Hydroxyphenyl)-5-(4-methoxyphenyl)-2,2-dimethylfuran-3(2H)-one (300 mg, 0.96 mmol) was added to a mixture of cesium carbonate (1.05 g, 3.8 mmol) and DMF (20 mL) at RT under nitrogen. The reaction mixture was stirred at RT for 30 minutes, upon which 6-chloro-2-(chloromethyl)imidazo[1,2-a]pyridine (201 mg, 1.4 mmol) was added. The mixture was heated at 80° C. for 4 h (the reaction was monitored by TLC). Upon completion of the reaction as judged by TLC, the reaction mixture was diluted with water and extracted with EtOAc. The combined organics were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography using 20% ethyl acetate in n-hexane and silica gel (230-400 mesh) to afford 4-(4-((6-chloroimidazo[1,2-a]pyridin-2-yl)methoxy)phenyl)-5-(4-methoxy phenyl)-2,2-dimethylfuran-3(2H)-one (180 mg, 39.3%,) as a white solid. 1H NMR, 500 MHz, DMSO-d6: δ 8.85 (s, 1H), 8.0 (s, 1H), 7.6 (d, 3H), 7.3 (d, 1H), 7.15 (d, 2H), 7.1 (d, 2H), 7.0 (d, 2H), 5.15 (s, 2H) 3.8 (s, 3H), 1.4 (s, 6H). MS: [M+H]+: m/z=475. HPLC: (98.0%, Condition-A).
Reaction SMILES: [CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][C:5]=1[N+]([O-])=O.C([Sn](CCCC)(CCCC)[CH:20]=[CH:21][O:22][CH2:23][CH3:24])CCC.O.CCOC(C)=O>O1CCOCC1>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([C:21]([O:22][CH2:23][CH3:24])=[CH2:20])=[CH:6][CH:5]=1
Reactant: COC(=O)c1ccc(Br)cc1[N+](=O)[O-]
Reactant: CCCC[Sn](C=COCC)(CCCC)CCCC
Solvent: CCOC(C)=O
Solvent: O
Solvent: C1COCCO1
Product: C=C(OCC)c1ccc(C(=O)OC)cc1
Temperature: 25 °C
Yield: 79 %

Procedure:
A solution of 4-bromo-2-nitro-benzoic acid methyl ester (10 g, 38.5 mmol) tetrakis-(triphenylphosphine)-palladium (4.44 g, 3.84 mmol), and tributyl-(ethoxyvinyl)-tin (21.5 g, 57.8 mmol) in dioxane (125 mL) was heated to 140° C. for 19 h. The mixture was allowed to cool to r.t., and then water and EtOAc were added. The aqueous phase was extracted with EtOAc (3×). The combined organic phases were dried (Na2SO4) and concentrated to dryness. The crude product was purified by flash chromatography (hexanes to EtOAc/hexanes (4:6) to give 4-(1-ethoxy-vinyl)-benzoic acid methyl ester (7.63 g, 30.4 mmol, 79%) as a brown solid. ES-MS: m/z 252 [M+H]+, rt 6.04 min
Reaction SMILES: [Br:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[C:4]([F:9])[CH:3]=1.[C:10]([O:14][C:15]([N:17]1[CH2:23][CH2:22][CH2:21][C@H:18]1[CH2:19]O)=[O:16])([CH3:13])([CH3:12])[CH3:11].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:19][CH:18]2[CH2:21][CH2:22][CH2:23][N:17]2[C:15]([O:14][C:10]([CH3:11])([CH3:13])[CH3:12])=[O:16])=[C:4]([F:9])[CH:3]=1
Reactant: Oc1ccc(Br)cc1F
Reactant: CC(C)(C)OC(=O)N1CCC[C@H]1CO
Agent: CC(C)OC(=O)/N=N/C(=O)OC(C)C
Agent: c1ccc(P(c2ccccc2)c2ccccc2)cc1
Solvent: C1CCOC1
Product: CC(C)(C)OC(=O)N1CCCC1COc1ccc(Br)cc1F
Temperature: 25 °C
Reaction time: 6 h
Yield: 73.3 %

Procedure:
To a stirred solution of 4-bromo-2-fluorophenol (217 ul, 2.002 mmol), N-tert-butoxycarbonyl prolinol (403 mg, 2.002 mmol), and Ph3P (630 mg, 2.403 mmol) in THF (7 mL) was added DIAD (477 ul, 2.423 mmol) at room temp. The resulting mixture was stirred for 6 hr at room temp and then overnight at 70° C. The mixture was concentrated in vacuo and the residue was chromatographed on silica-gel with n-hexane-EtOAc (5:1, v/v) as eluent to give 549.4 mg (73%) 1-bromo-4-[1-(tert-butoxycarbonyl)-2-pyrrolidinyl]methoxy-3-fluorobenzene as an oil. 1H-NMR (400 MHz, CDCl3) δ 1.46 (s, 9H), 1.85 (br m, 1H), 1.90–2.10 (br s, 3H), 3.30–3.47 (m, 2H), 3.85, 4.04 (br s each, 1H), 4.11–4.20 (m, 2H), 6.82–6.98 (m, 1H), 7.13–7.26 (m, 2H); MS (FAB) m/z 374 (M++1).
Reaction SMILES: Cl.[NH2:2][C@H:3]1[C:12]([CH2:15][CH3:16])([CH2:13][CH3:14])[C:11]2[CH:10]=[C:9]([OH:17])[CH:8]=[CH:7][C:6]=2[CH2:5][C@@H:4]1[O:18][CH3:19].[CH3:20][O:21][C:22](=[O:34])[C@H:23]([CH2:27][CH:28]1[CH2:33][CH2:32][CH2:31][CH2:30][CH2:29]1)[CH2:24][CH:25]=O.C(N(CC)CC)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl.CCOC(C)=O>[CH3:20][O:21][C:22](=[O:34])[C@H:23]([CH2:27][CH:28]1[CH2:29][CH2:30][CH2:31][CH2:32][CH2:33]1)[CH2:24][CH2:25][NH:2][C@@H:3]1[C@@H:4]([O:18][CH3:19])[CH2:5][C:6]2[C:11](=[CH:10][C:9]([OH:17])=[CH:8][CH:7]=2)[C:12]1([CH2:15][CH3:16])[CH2:13][CH3:14]
Reactant: CCC1(CC)c2cc(O)ccc2C[C@H](OC)[C@H]1N
Reactant: COC(=O)[C@@H](CC=O)CC1CCCCC1
Agent: CC(=O)O[BH-](OC(C)=O)OC(C)=O
Agent: Cl
Agent: [Na+]
Solvent: CCN(CC)CC
Solvent: ClCCl
Solvent: CCOC(C)=O
Product: CCC1(CC)c2cc(O)ccc2C[C@H](OC)[C@H]1NCC[C@@H](CC1CCCCC1)C(=O)OC
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 121.8 %

Procedure:
(6S,7S)-7-Amino-8,8-diethyl-6-methoxy-5,6,7,8-tetrahydro-naphthalen-2-ol hydrochloride salt (100 mg, 0.35 mmol), (R)-2-cyclohexylmethyl-4-oxo-butyric acid methyl ester (90 mg, 0.42 mmol) and triethylamine (35 mg, 0.035 mmol) were dissolved in dichloromethane (2.0 mL) and stirred at room temperature for 30 min. Sodium triacetoxyborohydride (1.03 g, 4.85 mmol) was added and the reaction was monitored by HPLC. After 3 h, additional (R)-2-cyclohexylmethyl-4-oxo-butyric acid methyl ester (20 mg, 0.1 mmol) and sodium triacetoxyborohydride (30 mg, 0.14 mmol) were added. Thirty minutes after the last addition, EtOAc (15 mL) was added and the mixture was washed with 5% aqueous sodium carbonate (2×5 mL) and saturated sodium chloride (5 mL). The organic layer was dried with Na2SO4) and concentrated to give the title compound (190 mg). (m/z): [M+H]+ calcd for C27H43NO4, 446.33; found, 446.6.
Reaction SMILES: [C:1]([C:3]1[CH:4]=[C:5]2[C:9](=[CH:10][CH:11]=1)[NH:8][C:7](=[O:12])[C:6]2=[C:13]([C:15]1[NH:16][CH:17]=[CH:18][CH:19]=1)C)#[N:2].C([SnH](CCCC)CCCC)CCC.[N-:33]=[N+:34]=[N-:35].[Na+]>C1(C)C=CC=CC=1.CO>[NH:2]1[C:1]([C:3]2[CH:4]=[C:5]3[C:9](=[CH:10][CH:11]=2)[NH:8][C:7](=[O:12])[C:6]3=[CH:13][C:15]2[NH:16][CH:17]=[CH:18][CH:19]=2)=[N:35][N:34]=[N:33]1
Reactant: [N-]=[N+]=[N-]
Reactant: CC(=C1C(=O)Nc2ccc(C#N)cc21)c1ccc[nH]1
Agent: CCCC[SnH](CCCC)CCCC
Agent: [Na+]
Solvent: CO
Solvent: Cc1ccccc1
Product: O=C1Nc2ccc(-c3nnn[nH]3)cc2C1=Cc1ccc[nH]1
Reaction time: 8 h

Procedure:
A solution of 5-cyano-3-[1-(pyrrol-2-yl)ethylidene]indolin-2-one (100 mg, 0,42 mmol) in toluene was treated with tributyltin hydride (0.68 g, 2.1 mmol) and NaN3 (0.39 g, 2.52 mmol). The reaction mixture was refluxed overnight. Concentration afforded a residue which was dissolved in methanol and left at ambient temperature overnight. An orange-colored solid formed, which was filtered and dried in vacuo to afford 5-tetrazol-5-yl-3-[(pyrrol-2-yl)methylene]indolin-2-one; (29 mg) as an orange solid; 1H NMR (400 MHz, DMSO-d6) δ 6.22 (s, 1H), 6.90 (s, 1H), 7.08 (d, 1H), 7.20 (s, 1H), 7.80 (m, 1H), 7.84 (s, 1H), 8.14 (s, 1H), 11.22 (s, 1H) ppm.
Reaction SMILES: [CH3:1][C:2]1[C:10]2[C:9]([NH2:11])=[CH:8][C:7]([CH3:12])=[N:6][C:5]=2[S:4][C:3]=1[C:13]1[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=1.CC(C)([O-])C.[Na+].[Cl:25][C:26]1[CH:27]=[C:28]([S:32](Cl)(=[O:34])=[O:33])[CH:29]=[CH:30][CH:31]=1>CN(C=O)C.C(OCC)(=O)C.O>[Cl:25][C:26]1[CH:27]=[C:28]([S:32]([NH:11][C:9]2[CH:8]=[C:7]([CH3:12])[N:6]=[C:5]3[S:4][C:3]([C:13]4[CH:14]=[N:15][CH:16]=[CH:17][CH:18]=4)=[C:2]([CH3:1])[C:10]=23)(=[O:34])=[O:33])[CH:29]=[CH:30][CH:31]=1
Reactant: O=S(=O)(Cl)c1cccc(Cl)c1
Reactant: Cc1cc(N)c2c(C)c(-c3cccnc3)sc2n1
Agent: CC(C)(C)[O-]
Agent: [Na+]
Solvent: CCOC(C)=O
Solvent: CN(C)C=O
Solvent: O
Product: Cc1cc(NS(=O)(=O)c2cccc(Cl)c2)c2c(C)c(-c3cccnc3)sc2n1
Temperature: 25 °C
Reaction time: 3 h
Yield: 23.5 %

Procedure:
To a stirred solution of 3,6-dimethyl-2-(3-pyridinyl)thieno[2,3-b]pyridin-4-amine (45 mg, 0.176 mmol) (Description 34) in DMF (1.5 mL) was added sodium tert-butoxide (42.3 mg, 0.441 mmol) and 3-chlorobenzenesulfonyl chloride (0.050 mL, 0.352 mmol). The reaction mixture was stirred at RT under nitrogen for 3 h and then diluted with ethyl acetate (20 mL) and water (30 mL). The organic layer was separated and the aqueous layer re-extracted with ethyl acetate (2×15 mL). The combined organic layers were dried over Na2SO4 and concentrated. Purification by chromatography on silica gel, eluting with a gradient of 0-100% ethyl acetate in DCM was followed by further purification by MDAP (acidic conditions), to afford the title compound (17.8 mg). LCMS (A) m/z: 430 [M+1]+, Rt 1.06 min (acidic), Rt 0.86 min (basic).
Reaction SMILES: [Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6](=O)[C:7](=[O:28])[N:8]2[CH2:11][C:12]([N:14]2[CH2:19][CH2:18][N:17]([N:20]=CC3C=CC=CC=3)[CH2:16][CH2:15]2)=[O:13])=[CH:4][CH:3]=1.Cl.[NH2:31][OH:32].O>C(#N)C.Cl>[ClH:1].[Cl:1][C:2]1[CH:10]=[C:9]2[C:5]([C:6](=[N:31][OH:32])[C:7](=[O:28])[N:8]2[CH2:11][C:12]([N:14]2[CH2:19][CH2:18][N:17]([NH2:20])[CH2:16][CH2:15]2)=[O:13])=[CH:4][CH:3]=1
Reactant: O=C1C(=O)N(CC(=O)N2CCN(N=Cc3ccccc3)CC2)c2cc(Cl)ccc21
Reactant: NO
Agent: Cl
Solvent: O
Solvent: CC#N
Product: NN1CCN(C(=O)CN2C(=O)C(=NO)c3ccc(Cl)cc32)CC1
Temperature: 40 °C
Yield: 79 %

Procedure:
A mixture of 6-chloro-1-[(4-benzylideneamino-1-piperazinyl)carbonylmethyl]-2,3-indolinedione (1.5 g) and hydroxylamine hydrochloride (2.5 g) in acetonitrile (100 ml), conc. hydrochloric acid (50 ml), and water (50 ml) was heated at 40° C. for 2 hour. The reaction mixture was concentrated up to 20 ml and the precipitates appeared were filtered, and air-dried. This crude material was recrystallized from aqueous methanol at first, and for water finally to give 6-chloro-1-[(4-amino-1-piperazinyl)carbonylmethyl]-3-hydroxyimino-2-indolinone hydrochloride (0.54 g).
Reaction SMILES: [C:1]1(=[O:7])[O:6][C:4](=[O:5])[CH:3]=[CH:2]1.[OH-:8].[Ca+2:9].[OH-].[CH3:11]O>>[CH3:11]/[C:2](=[CH:3]/[C:4]([O-:8])=[O:5])/[C:1]([O-:6])=[O:7].[CH3:11]/[C:2](=[CH:3]/[C:4]([O-:8])=[O:5])/[C:1]([O-:6])=[O:7].[Ca+2:9].[Ca+2:9]
Reactant: CO
Reactant: [OH-]
Reactant: O=C1C=CC(=O)O1
Agent: [Ca+2]
Product: C/C(=C/C(=O)[O-])C(=O)[O-]
Temperature: 25 °C

Procedure:
One mole of maleic anhydride is dissolved with stirring in 1000 ml methanol at 50°-60° C. The mixture is cooled to 25° C. and with the aid of a pH meter, the pH is adjusted to 8.6 with calcium hydroxide while maintaining the temperature below 25° C. with an ice bath. 149 g of calcium bis(methyl maleate) is recovered by crystallizing out of methanol followed by drying in a vacuum oven.
Reaction SMILES: [CH2:1]([N:3]1[C:11]2[C:6](=[CH:7][C:8]([O:12]CC=C)=[CH:9][CH:10]=2)[CH2:5][C:4]1=[O:16])[CH3:2].C(N(CC)[C:20]1[CH:25]=CC=C[CH:21]=1)C>>[CH2:1]([N:3]1[C:11]2[C:6](=[C:7]([CH2:25][CH:20]=[CH2:21])[C:8]([OH:12])=[CH:9][CH:10]=2)[CH2:5][C:4]1=[O:16])[CH3:2]
Reactant: CCN(CC)c1ccccc1
Reactant: C=CCOc1ccc2c(c1)CC(=O)N2CC
Product: C=CCc1c(O)ccc2c1CC(=O)N2CC
Temperature: 0 °C
Yield: 12 %

Procedure:
A solution of 1.09 g. (5.02 mmoles) of 1-ethyl-5-allyloxyoxindole in 5 ml. of N,N-diethylaniline was heated at reflux for 1 hour. The cooled reaction was added to ice cold 1N hydrochloric acid and the mixture extracted with methylene chloride. The extract was washed with water (3×), saturated brine solution (1×) and dried over magnesium sulfate. The residue remaining after the solvent was removed was chromatographed on 22 g. of silica gel using 50-100% diethyl ether-hexane as the eluent to give 134 mg. (12% yield) of 1-ethyl-4-allyl-5-hydroxyoxindole and 644 mg. (59% yield) of 1-ethyl-5-hydroxy-6-allyloxindole, m.p. 130°-131° C.
Reaction SMILES: [CH2:1]([O:3][Si:4]([C:11]12[CH2:17][CH:14]([CH2:15][CH2:16]1)[CH:13]=[CH:12]2)([O:8][CH2:9][CH3:10])[O:5][CH2:6][CH3:7])[CH3:2].C([SiH](CC)CC)C.C(O)C.[C:28]1(C)[CH:33]=CC=[CH:30][CH:29]=1>ClCCl.C1COCC1>[CH2:33]([C:11]12[CH2:17][CH:14]([CH2:15][CH2:16]1)[CH:13]=[CH:12]2)[CH2:28][CH2:29][CH3:30].[CH2:6]([O:5][Si:4]([C:11]12[CH2:17][CH:14]([CH2:15][CH2:16]1)[CH:13]=[CH:12]2)([O:8][CH2:9][CH3:10])[O:3][CH2:1][CH3:2])[CH3:7]
Reactant: Cc1ccccc1
Agent: CCO[Si](OCC)(OCC)C12C=CC(CC1)C2
Agent: CC[SiH](CC)CC
Solvent: CCO
Solvent: C1CCOC1
Solvent: ClCCl
Product: CCCCC12C=CC(CC1)C2
Temperature: 80 °C

Procedure:
BuNB (25.22 g, 0.168 mol), Triethoxysilyl Norbomene (TESNB, CAS 18401-43-9) (4.78 g, 0.019 mol), triethyl silane (0.11 g, 9.32E-05 mol), ethanol (0.10 g, 2.24E-03 mol) and toluene (170.0 g) were combined in a 500 mL serum bottle and heated to 80° C. in an oil bath to form a solution. To this solution were injected Pd1206 (0.018 g, 1.49E-05 mol) in the form of a concentrated solution in dichloromethane. After addition, the resulting mixture was maintained at 80° C. for 9 hours. The copolymer was precipitated by adding methanol drop wise into the vigorously stirred reaction mixture. The precipitated copolymer was collected by filtration and dried in an oven at 60° C. under vacuum After drying, 20.58 g was obtained (69%). The molecular weight of the copolymer was determined by GPC in THF solvent (polystyrene standard) to be Mw=238,000 and Mn=96,000. The composition of the copolymer was determined by 1H-NMR to be (85/15) BuNB/TESNB copolymer. The refractive indices of this polymer were measured by prism coupling method and determined to be 1.5061 in TE mode and 1.5041 in TM mode at a wavelength of 633 nm. The Tg (based on thermomechanical analysis (TMA) measurement) of this polymer was 276° C. The dried copolymer was dissolved insufficient toluene to result in a 30 wt % copolymer solution.
Reaction SMILES: CN(C(ON1N=N[C:11]2C=CC=N[C:10]1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.[Br:25][C:26]1[CH:27]=[C:28]([NH:33][CH2:34][CH3:35])[C:29]([NH2:32])=[CH:30][CH:31]=1.[CH:36](N(CC)C(C)C)(C)[CH3:37].C1(C(O)=O)CC1>CN(C=O)C>[Br:25][C:26]1[CH:31]=[CH:30][C:29]2[N:32]=[C:34]([CH:35]3[CH2:11][CH2:10]3)[N:33]([CH2:36][CH3:37])[C:28]=2[CH:27]=1
Reactant: CCN(C(C)C)C(C)C
Reactant: CN(C)C(On1nnc2cccnc21)=[N+](C)C
Reactant: CCNc1cc(Br)ccc1N
Agent: F[P-](F)(F)(F)(F)F
Agent: O=C(O)C1CC1
Solvent: CN(C)C=O
Product: CCn1c(C2CC2)nc2ccc(Br)cc21
Temperature: 25 °C
Reaction time: 1 h

Procedure:
HATU (4.89 g) was added to a solution of 4-bromo-N2-ethylbenzene-1,2-diamine (2.63 g), N,N-diisopropylethylamine (6.40 ml) and cyclopropanecarboxylic acid (0.979 ml) in DMF (40 ml) at room temperature. The mixture was stirred at room temperature for 1 h. The mixture was quenched with water and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was dissolved into AcOH (40.0 ml), and the mixture was stirred at 80° C. for 1 h. After concentration of the mixture, the residue was neutralized with saturated NaHCO3 solution and extracted with EtOAc. The organic layer was separated, washed with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (hexane/EtOAc) to give the title compound (1.2 g) as a pale yellow solid.
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]([CH2:11][C:12]([O:14]CC)=O)=[O:10])=[CH:4][CH:3]=1.[ClH:17].[NH2:18][OH:19].[Na]>CO>[ClH:17].[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9]([CH2:11][C:12]([NH:18][OH:19])=[O:14])=[O:10])=[CH:4][CH:3]=1
Reactant: NO
Reactant: CCOC(=O)CC(=O)Nc1ccc(N)cc1
Agent: Cl
Agent: [Na]
Solvent: CO
Product: Nc1ccc(NC(=O)CC(=O)NO)cc1
Reaction time: 2 h
Yield: 64 %

Procedure:
A mixture of 17.8 g (0.08 mol) of ethyl 4-aminophenylcarbamoylacetate, 7 g (0.1 mol) of hydroxylamine hydrochloride and 4.6 g (0.2 gram atom) of sodium in 250 ml of anhydrous methanol is left in contact for 2 hours at 20° C. The methanol is evaporated in vacuo, the residue is taken up in 100 ml of water and acidified with 6 N HCl and the product is filtered off. Recrystallisation from 80 ml of water gives CRL 40,472. Melting point 164°-165° C. (with decomposition). Yield: 64%.
Reaction SMILES: [O:1]=[C:2]1[NH:16][C:5]2=[CH:6][C:7]3[CH:8]=[C:9]([C:13]([OH:15])=O)[NH:10][C:11]=3[CH:12]=[C:4]2[NH:3]1.[CH2:17]([CH:24]1[CH2:29][CH2:28][NH:27][CH2:26][CH2:25]1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C(#N)C>[CH2:17]([CH:24]1[CH2:29][CH2:28][N:27]([C:13]([C:9]2[NH:10][C:11]3[CH:12]=[C:4]4[NH:3][C:2](=[O:1])[NH:16][C:5]4=[CH:6][C:7]=3[CH:8]=2)=[O:15])[CH2:26][CH2:25]1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1
Reactant: O=C(O)c1cc2cc3[nH]c(=O)[nH]c3cc2[nH]1
Reactant: c1ccc(CC2CCNCC2)cc1
Solvent: CC#N
Product: O=C(c1cc2cc3[nH]c(=O)[nH]c3cc2[nH]1)N1CCC(Cc2ccccc2)CC1

Procedure:
The title compound is prepared from 2-oxo-1,2,3,5-tetrahydro-imidazo[4,5-f]indole-6-carboxylic acid and 4-benzylpiperidine according to the method described in Example 1/c. Mp.: >270° C. (acetonitrile).
Reaction SMILES: [NH:1]1[C:9]2[C:4](=[CH:5][C:6]([C:10]([O:12][CH3:13])=[O:11])=[CH:7][CH:8]=2)[CH:3]=[CH:2]1.[H-].[Na+].Br[CH2:17][CH2:18][O:19][CH3:20]>O>[CH3:20][O:19][CH2:18][CH2:17][N:1]1[C:9]2[C:4](=[CH:5][C:6]([C:10]([O:12][CH3:13])=[O:11])=[CH:7][CH:8]=2)[CH:3]=[CH:2]1
Reactant: COC(=O)c1ccc2[nH]ccc2c1
Reactant: COCCBr
Agent: [H-]
Agent: [Na+]
Solvent: O
Product: COCCn1ccc2cc(C(=O)OC)ccc21
Temperature: 60 °C
Reaction time: 2 h
Yield: 49.6 %

Procedure:
To a stirred solution of methyl 1H-indole-5-carboxylate (200 mg, 1.14 mmol) and sodium hydride (60% in oil, 39 mg, 1.71 mmol) in N,N-dimethylformanide (3 mL) was added 1-bromo-2-methoxyethane (190 mg, 1.37 mmol) at room temperature. Then the mixture was stirred at 60° C. for 2 hours. The mixture was poured into water (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with water (20 mL) and dried over sodium sulfate. After removal of the solvent, the residue was purified by column chromatography on silica gel eluting with n-hexane/ethyl acetate (2:1) to give 132 mg (50%) of the title compound as colorless syrup.
Reaction SMILES: [CH2:1]([O:3][C:4](=[O:68])[CH:5]=[CH:6][C@H:7]([CH3:67])[C@H:8]([O:57][CH2:58][C:59]1[CH:64]=[CH:63][C:62]([O:65][CH3:66])=[CH:61][CH:60]=1)[C@@H:9]([CH3:56])[CH:10]=[CH:11][C@@H:12]([O:48][Si:49]([C:52]([CH3:55])([CH3:54])[CH3:53])([CH3:51])[CH3:50])[CH2:13][C@H:14]([O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:43])[CH3:42])[C@H:15]([CH3:39])[CH:16]=[CH:17][CH2:18][O:19][C:20]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH3:2].[BH4-].[Na+]>CO.C1COCC1>[CH2:1]([O:3][C:4](=[O:68])[CH2:5][CH2:6][C@H:7]([CH3:67])[C@@H:8]([O:57][CH2:58][C:59]1[CH:64]=[CH:63][C:62]([O:65][CH3:66])=[CH:61][CH:60]=1)[C@@H:9]([CH3:56])[CH:10]=[CH:11][C@@H:12]([O:48][Si:49]([C:52]([CH3:53])([CH3:54])[CH3:55])([CH3:50])[CH3:51])[CH2:13][C@H:14]([O:40][Si:41]([C:44]([CH3:47])([CH3:46])[CH3:45])([CH3:42])[CH3:43])[C@H:15]([CH3:39])[CH:16]=[CH:17][CH2:18][O:19][C:20]([C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1)([C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH3:2]
Reactant: CCOC(=O)C=C[C@H](C)[C@H](OCc1ccc(OC)cc1)[C@@H](C)C=C[C@H](C[C@H](O[Si](C)(C)C(C)(C)C)[C@H](C)C=CCOC(c1ccccc1)(c1ccccc1)c1ccccc1)O[Si](C)(C)C(C)(C)C
Agent: [BH4-]
Agent: [Na+]
Solvent: CO
Solvent: C1CCOC1
Product: CCOC(=O)CC[C@H](C)[C@@H](OCc1ccc(OC)cc1)[C@@H](C)C=C[C@H](C[C@H](O[Si](C)(C)C(C)(C)C)[C@H](C)C=CCOC(c1ccccc1)(c1ccccc1)c1ccccc1)O[Si](C)(C)C(C)(C)C
Reaction time: 1 h
Yield: 0.1 %

Procedure:
To a stirred solution of unsaturated ester 65 (2.02 g, 2.10 □mol) in MeOH (10 ml), THF (1 ml) at 0° C. was added 0.25 g of NiCl26H2O then portionwise NaBH4 (0.16 g). After 1 h, the reaction mixture was evaporated and filtered with Celite using Et2O as an eluent (5 ml). The organic phase was concentrated and the residue was purified by flash chromatography (EtOAc/Hexane 1:9) to yield 1.96 g (2.04 μmol) of product 66 (97%) as a colorless oil: IR (CHCl3) 2956, 2929, 2856, 1735, 1613, 1514, 1479, 1448, 1374, 1249, 1174, 1072, 836, 773, 706 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.53 (m, 6H), 7.33 (m, 1H), 6.84 (m, 2H), 5.81 (dd, J=15.7, 6.1 Hz, 1H), 5.65 (m, 1H), 5.45 (m, 2H), 4.65 (m, 1H), 4.56 (d, J=10.9 Hz, 1H), 4.45 (d, J=10.9 Hz, 1H), 4.14 (q, J=7.1 Hz, 2H), 3.96 (m, 1H), 3.80 (s, 3H), 3.62 (m, 2H), 3.14 (m, 1H), 2.79 (m, 1H), 2.43 (m, 1H), 2.23 (m, 1H), 1.72 (m, 2H), 1.54 (m, 3H), 1.28 (t, J=7.1 Hz, 3H), 1.06 (d, J=6.7 Hz, 3H), 1.01 (d, J=6.9 Hz, 3H), 0.97 (s, 18H), 0.93 (d, J=6.4 Hz, 3H), 0.17 (s, 3H), 0.154 (s, 3H), 0.151 (s, 3H), 0.14 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 173.6, 158.8, 144.4, 134.6, 133.6, 132.1, 131.2, 129.1, 128.7, 127.7, 126.8, 126.4, 103.4, 86.6, 86.1, 73.8, 72.8, 66.5, 65.2, 60.0, 55.1, 42.8, 42.3, 35.4, 35.1, 32.3, 29.4, 26.0, 25.9, 18.4, 18.1, 14.6, 14.2, 13.9, −2.9, −4.0, −4.1; HRMS (ESI) calcd for C59H86O7Si2K 1001.5549 (M+K)+, found 1001.5586; [α]20D −9.8 (c 0.95, CHCl3).
Reaction SMILES: Cl[C:2]([O:4][CH3:5])=[O:3].[NH2:6][CH:7]([CH2:11][CH2:12][S:13]([CH3:16])(=[O:15])=[O:14])[C:8]([OH:10])=[O:9].[OH-].[Na+].O>C1COCC1>[CH3:16][S:13]([CH2:12][CH2:11][CH:7]([NH:6][C:2]([O:4][CH3:5])=[O:3])[C:8]([OH:10])=[O:9])(=[O:14])=[O:15]
Reactant: COC(=O)Cl
Reactant: CS(=O)(=O)CCC(N)C(=O)O
Agent: [Na+]
Agent: [OH-]
Solvent: C1CCOC1
Solvent: O
Product: COC(=O)NC(CCS(C)(=O)=O)C(=O)O
Temperature: 25 °C
Reaction time: 9 h
Yield: 14.6 %

Procedure:
Methyl chloroformate (2.6 mL, 33 mmol) was added dropwise to a stirred suspension of 2-Amino-4-methanesulfonyl-butyric acid (5.03 g, 27.8 mmol) and NaOH (5 N in H2O, 13.3 mL, 66.6 mmol) in THF (50 mL). After stirring at room temperature for 9 h, additional methyl chloroformate (5.2 mL, 66.6 mmol) and NaOH (5 N in H2O, 30 mL, 150 mmol) were added. After another 14 h, the reaction mixture was poured into H2O. The aqueous phase was washed with DCM 2× then acidified to pH 1 with 10% HCl. The acidified aqueous phase was extracted 3× with EtOAc. The combined organics were dried over MgSO4, filtered and concentrated to provide 4-Methanesulfonyl-2-methoxycarbonylamino-butyric acid (970 mg, 15%).