Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [H-].[Na+].[N+:3]([C:6]1[CH:7]=[C:8]2[NH:14][C:13](=[O:15])[O:12][C:10](=[O:11])[C:9]2=[CH:16][CH:17]=1)([O-:5])=[O:4].[CH3:18]I.Cl>CN(C=O)C>[CH3:18][N:14]1[C:13](=[O:15])[O:12][C:10](=[O:11])[C:9]2[CH:16]=[CH:17][C:6]([N+:3]([O-:5])=[O:4])=[CH:7][C:8]1=2
Reactant: CI
Reactant: O=c1[nH]c2cc([N+](=O)[O-])ccc2c(=O)o1
Agent: Cl
Agent: [H-]
Agent: [Na+]
Solvent: CN(C)C=O
Product: Cn1c(=O)oc(=O)c2ccc([N+](=O)[O-])cc21
Temperature: 25 °C
Yield: 86.7 %

Procedure:
To a suspension of 0.1656 g (4.14 mmoles) of sodium hydride (60% in mineral oil) in 20 mL DMF was added a solution of 0.6584 g (3.16 mmoles) of 4-nitroisatoic anhydride in 20 mL DMF. After stirring a few minutes at room temperature, a clear orange solution formed. 0.2615 g (3.2 mmoles) of methyl iodide was added to the reaction, and the mixture was stirred at room temperature for 4 hours. The reaction was poured into 50 mL of cold 1 N HCl, and the resulting bright orange precipitate was filtered and washed sequentially with water and ether to give 608.3 mg (86%) of product. 1H NMR (CO(CD3)2, 400 MHz,) δ 3.69 (s, 3H, —NCH3—), 8.12 (dd, J=8.8 Hz, 2 Hz, 1H, ArH), 8.2 (d, J=2 Hz, 1H, ArH), 8.34 (d, J=8.4 Hz, 1H, ArH).
Reaction SMILES: [C:1]1([PH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH:14]([Si:16]([O:21][CH3:22])([O:19][CH3:20])[O:17][CH3:18])=[CH2:15].C(OOC(C)(C)C)(C)(C)C>C(O)(C)C>[C:8]1([P:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[CH2:15][CH2:14][Si:16]([O:21][CH3:22])([O:19][CH3:20])[O:17][CH3:18])[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1
Reactant: c1ccc(Pc2ccccc2)cc1
Reactant: C=C[Si](OC)(OC)OC
Agent: CC(C)(C)OOC(C)(C)C
Solvent: CC(C)O
Product: CO[Si](CCP(c1ccccc1)c1ccccc1)(OC)OC
Reaction time: 100 h

Procedure:
A solution of 2-(diphenylphosphino)ethyltrimethoxysilane (DPETMS) in isopropanol comprising 12% DPETMS and 88% isopropanol and 2-4 drops titanium acetylacetonate dialkoxide in alcohol was prepared. The DPETMS was synthesized by combining diphenylphosphine and vinyltrimethoxysilane in a borosilicate flask and then exposing to sunlight for 100 hours, or by using t-butylperoxide or azodiisobutryronitrile as a catalyst. Excess volatile material was removed in vacuo at 1-2 mmHg pressure and the remaining material tested.
Reaction SMILES: [Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:12][O:11][C:10]3[CH:13]=[CH:14][C:15]([Cl:17])=[CH:16][C:9]=3[NH:8][CH2:7][C:6]=2[CH:18]=1.[C:19](OC(=O)C)(=[O:21])[CH3:20].N1C=CC=CC=1>CN(C1C=CN=CC=1)C.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:12][O:11][C:10]3[CH:13]=[CH:14][C:15]([Cl:17])=[CH:16][C:9]=3[N:8]([C:19](=[O:21])[CH3:20])[CH2:7][C:6]=2[CH:18]=1
Reactant: Clc1ccc2c(c1)NCc1cc(Br)ccc1CO2
Reactant: CC(=O)OC(C)=O
Agent: CN(C)c1ccncc1
Solvent: Cc1ccccc1
Solvent: c1ccncc1
Product: CC(=O)N1Cc2cc(Br)ccc2COc2ccc(Cl)cc21
Temperature: 70 °C
Yield: 96 %

Procedure:
To a stirred solution of 9-Bromo-2-chloro-11,12-dihydro-6H-5-oxa-12-aza-dibenzo[a,e]cyclooctene Example 347E (3.8 mg, 11.7 umol) and DMAP (cat. amount) in toluene (0.3 mL) was added acetic anhydride (0.10 mL, 1.05 mmol) and pyridine (0.05 mL, 46.9 umol). This reaction mixture was heated at 70° C. for 30 minutes, cooled to room temperature and concentrated in vacuo. This was purified by a ISCO auto CombiFlash with a RediSep 4 g column, eluted with Hexane-CH2Cl2, detected at 220 nM to give 4.1 mg of 1-(9-Bromo-2-chloro-6,11-dihydro-5-oxa-12-aza-dibenzo[a,e]cycloocten-12-yl)-ethanone Example 347E in 96% yield. HPLC Rt=3.56 min (YMC S5 ODS column 4.6×50 mm, 10-90% aqueous methanol over 4 minutes containing 0.2% phosphoric acid, 4 mL/min, monitoring at 220 nm) LC/MS: M+H=366.
Reaction SMILES: C[CH:2]([CH3:6])[CH2:3][CH2:4][NH2:5].[N:7]1[CH:8]=[CH:9][N:10]2[CH:15]=[C:14]([CH2:16][NH:17][C:18]([C:20]3[CH:28]=[CH:27][C:23]([C:24]([OH:26])=O)=[CH:22][CH:21]=3)=[O:19])[CH:13]=[CH:12][C:11]=12.[N+](C1C=CC([C:36](O)=[O:37])=CC=1)([O-])=O>>[N:7]1[CH:8]=[CH:9][N:10]2[CH:15]=[C:14]([CH2:16][NH:17][C:18]([C:20]3[CH:21]=[CH:22][C:23]([C:24]([NH:5][CH2:4][C@@H:3]4[CH2:2][CH2:6][O:37][CH2:36]4)=[O:26])=[CH:27][CH:28]=3)=[O:19])[CH:13]=[CH:12][C:11]=12
Reactant: O=C(O)c1ccc([N+](=O)[O-])cc1
Reactant: CC(C)CCN
Reactant: O=C(O)c1ccc(C(=O)NCc2ccc3nccn3c2)cc1
Product: O=C(NCc1ccc2nccn2c1)c1ccc(C(=O)NC[C@@H]2CCOC2)cc1

Procedure:
The title compound was prepared as described in Example 1A, substituting (5)-(tetrahydrofuran-3-yl)methanamine for 3-methylbutan-1-amine and 4-(imidazo[1,2-a]pyridin-6-ylmethylcarbamoyl)benzoic acid for 4-nitrobenzoic acid. 1H NMR (300 MHz, DMSO-d6) δ ppm 9.15 (t, J=5.8 Hz, 1H), 8.68 (t, J=5.7 Hz, 1H), 8.49 (bs, 1H), 8.03-7.85 (m, 5H), 7.58-7.50 (m, 2H), 7.23 (dd, J=9.1, 1.7 Hz, 1H), 4.49 (d, J=5.8 Hz, 2H), 3.80-3.56 (m, 4H), 3.48 (dd, J=8.5, 5.2 Hz, 1H), 3.28-3.17 (m, 1H), 2.03-1.87 (m, 1H), 1.68-1.46 (m, 1H), 1.37-1.09 (m, 1H); MS (ESI(+)) m/e 379 (M+H)+.
Reaction SMILES: [CH:1]1([N:4]([CH:20]([C:22]2[CH:30]=[C:29]([O:31][CH2:32][CH2:33][CH2:34][O:35][CH3:36])[C:25]3[CH:26]=[CH:27][O:28][C:24]=3[CH:23]=2)[CH3:21])[C:5]([C@@H:7]2[O:12][CH2:11][CH2:10][N:9](C(OC(C)(C)C)=O)[CH2:8]2)=[O:6])[CH2:3][CH2:2]1.N1C(C)=CC=CC=1C.C[Si](OS(C(F)(F)F)(=O)=O)(C)C.C(=O)([O-])O.[Na+]>C(Cl)(Cl)Cl>[CH:1]1([N:4]([C@@H:20]([C:22]2[CH:30]=[C:29]([O:31][CH2:32][CH2:33][CH2:34][O:35][CH3:36])[C:25]3[CH:26]=[CH:27][O:28][C:24]=3[CH:23]=2)[CH3:21])[C:5]([C@@H:7]2[O:12][CH2:11][CH2:10][NH:9][CH2:8]2)=[O:6])[CH2:3][CH2:2]1.[CH:1]1([N:4]([C@H:20]([C:22]2[CH:30]=[C:29]([O:31][CH2:32][CH2:33][CH2:34][O:35][CH3:36])[C:25]3[CH:26]=[CH:27][O:28][C:24]=3[CH:23]=2)[CH3:21])[C:5]([C@@H:7]2[O:12][CH2:11][CH2:10][NH:9][CH2:8]2)=[O:6])[CH2:3][CH2:2]1
Reactant: COCCCOc1cc(C(C)N(C(=O)[C@H]2CN(C(=O)OC(C)(C)C)CCO2)C2CC2)cc2occc12
Agent: C[Si](C)(C)OS(=O)(=O)C(F)(F)F
Agent: O=C([O-])O
Agent: [Na+]
Solvent: ClC(Cl)Cl
Solvent: Cc1cccc(C)n1
Product: COCCCOc1cc([C@@H](C)N(C(=O)[C@H]2CNCCO2)C2CC2)cc2occc12
Product: COCCCOc1cc([C@H](C)N(C(=O)[C@H]2CNCCO2)C2CC2)cc2occc12
Reaction time: 0.5 h

Procedure:
To a solution of tert-butyl (2R)-2-[(cyclopropyl{1-[4-(3-methoxypropoxy)-1-benzofuran-6-yl]ethyl}amino)carbonyl]morpholine-4-carboxylate (200 mg) and 2,6-lutidine (0.142 mL) in chloroform (4 mL) was added trimethylsilyltriflate (0.180 mL) under ice-cooling, and the mixture was stirred at the same temperature for 30 minutes. Then, thereto was added aqueous saturated sodium hydrogen carbonate solution under ice-cooling, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent: chloroform/methanol/ammonia water=200/2/1) to give (2R)-N-cyclopropyl-N-{(1R)-1-[4-(3-methoxypropoxy)-1-benzofuran-6-yl]ethyl}morpholine-2-carboxamide [Ex(1-1)] (12.5 mg) and (2R)-N-cyclopropyl-N-{(1S)-1-[4-(3-methoxypropoxy)-1-benzofuran-6-yl]ethyl}morpholine-2-carboxamide [Ex(1-2)] (20.2 mg) as a colorless oil.
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:26])[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[NH:16][C:17]([O:19][CH:20]2[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]2)=[O:18])=[N:6][CH:7]=1.[C:27]1(=O)[CH2:31][CH2:30][CH2:29][CH2:28]1.C([BH3-])#N.[Na+].Cl>>[ClH:1].[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([NH:8][C:9](=[O:26])[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=2[NH:16][C:17]([O:19][CH:20]2[CH2:21][CH2:22][N:23]([CH:27]3[CH2:31][CH2:30][CH2:29][CH2:28]3)[CH2:24][CH2:25]2)=[O:18])=[N:6][CH:7]=1
Reactant: O=C1CCCC1
Reactant: O=C(Nc1ccccc1C(=O)Nc1ccc(Cl)cn1)OC1CCNCC1
Agent: Cl
Agent: [BH3-]C#N
Agent: [Na+]
Product: O=C(Nc1ccccc1C(=O)Nc1ccc(Cl)cn1)OC1CCN(C2CCCC2)CC1
Yield: 122.1 %

Procedure:
Using a similar procedure to that described in Example 9-C, N-(5-chloropyridin-2-yl)-2-[(piperidin-4-yloxycarbonyl)amino]benzamide (100 mg, 0.205 mmol), cyclopentanone (0.091 mL, 1.02 mmol), and sodium cyanoborohydride (51 mg, 0.82 mmol) yielded, after treatment with HCl, 60 mg (60%) of the title compound as a hydrochloride salt.
Reaction SMILES: Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]1[CH2:10][CH:9]1[CH:11]1[CH2:13][CH2:12]1.[CH2:14]([NH2:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C([O-])(C)(C)C.[Na+].C(OCC)(=O)C>C(COC)OC>[CH2:14]([NH:21][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]1[CH2:10][CH:9]1[CH:11]1[CH2:13][CH2:12]1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1
Reactant: Clc1ccccc1C1CC1C1CC1
Reactant: NCc1ccccc1
Agent: CC(C)(C)[O-]
Agent: [Na+]
Solvent: CCOC(C)=O
Solvent: COCCOC
Product: c1ccc(CNc2ccccc2C2CC2C2CC2)cc1
Reaction time: 24 h
Yield: 87.1 %

Procedure:
3 g of 2-(2-chlorophenyl)bicyclopropyl (15.6 mmol, trans/cis ratio of about 2:1), 2.5 g of benzylamine (23.4 mmol), 2.4 g of sodium tert-butanolate (25 mmol), 35 mg of Pd(II) acetate (0.16 mmol) and 60 mg of R(−)-di-tert-butyl-[1-[(S)-2-(dicyclohexylphosphanyl)-ferrocenyl]ethyl]phosphine (0.11 mmol) are dissolved in 30 ml of dimethoxyethane. The reaction mixture is heated to the reflux temperature of the solvent and is stirred for 24 hours. After cooling, ethyl acetate is added and the organic phase is washed with water. The solvent is removed using a water jet vacuum and the residue is dried. The product is purified by column chromatography on silica gel (eluant:ethyl acetate/hexane 1:15). 3.58 g of benzyl(2-bicyclopropyl-2-yl-phenyl)amine (87% of theory) are obtained in the form of a brown oil (trans/cis ratio of about 2:1).