Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [CH3:1][CH2:2]/[CH:3]=[CH:4]/[CH2:5][CH3:6].[Na]N(Cl)S(=O)=O.[CH3:13][C:14]1[CH:15]=[CH:16][C:17]([S:20]([NH:23]Cl)(=[O:22])=[O:21])=[CH:18][CH:19]=1.CC1C=CC(S([N-]Cl)(=O)=O)=CC=1.O.O.O.[Na+].CC(O)C([O-])=O.C1C=CC([Hg+])=CC=1.C(N(CCO)CCO)CO>CC#N>[CH2:2]([C@H:3]1[C@H:4]([CH2:5][CH3:6])[N:23]1[S:20]([C:17]1[CH:18]=[CH:19][C:14]([CH3:13])=[CH:15][CH:16]=1)(=[O:21])=[O:22])[CH3:1]
Reactant: Cc1ccc(S(=O)(=O)NCl)cc1
Reactant: CC/C=C/CC
Agent: CC(O)C(=O)[O-]
Agent: Cc1ccc(S(=O)(=O)[N-]Cl)cc1
Agent: O=[SH](=O)N([Na])Cl
Solvent: CC#N
Solvent: OCCN(CCO)CCO
Solvent: O
Product: CC[C@H]1[C@H](CC)N1S(=O)(=O)c1ccc(C)cc1
Reaction time: 24 h
Yield: 93 %

Procedure:
General procedure (described for trans-3-hexene) as illustrated in FIG. 2, entry 1: To a mixture of trans-3-hexene (252 mg, 3 mmol; see above discussion for employable olefins (FIG. 1); 1.0 equivalents used) and anhydrous N-sodio-N-chloro sulfonamide (chloramine T/751 mg, 3.3 mmol; see above discussion for employable salts or chloramine trihydrates (chloramine T trihydrate can be effectively used in the same concentration); effective range: 1.0-2.0 equivalents; optimal concentration 1.1 equivalents) in CH3CN (15 ml, 0.2 Molar; see above discussion for employable solvents; effective range: 0.01 Molar to 1.0 Molar) was added PTAB (113 mg, 0.3 mmol; effective range: 0.05 to 0.50 equivalents; optimal concentration: 0.10 equivalents) at 25° C. (effective range 25° C. to 60° C.). After vigorous stirring for 12 h (time can vary from 1 h- to 24 h depending on scale and substrate). The reaction mixture was worked up using standard workup conditions. A typical procedure may be carried out as follows: The reaction mixture was concentrated (about up to 1/10 volume) and filtered through a short column of silica gel (4×4 cm, 10% EtOAc in hexane). After evaporation of the solvent, the resultant solid was purified by recrystallization in hexane to give 710 mg (93%) of trans-2,3-diethyl-1-[(4-methylphenyl)sulfonyl]aziridine as colorless crystals; 1H NMR (CDCl3400 MHz)δ7.81 (d, J=8.2 Hz, 2H), 7.28 (d, J=8.2 Hz, 2H), 2.56-2.61 (m, 2H), 2.40 (s, 3H), 1.63-1.79 (m, 4H), 0.90 (t, J=7.5 Hz, 6H); 13C NMR (CDCl3, 100 MHz) d 143.7, 137.9, 129.4, 127.4, 50.9, 23.2, 21.5, 11.7; MS (FAB, NBA/NaI): 254 (M+H)+; HRMS (FAB, NBA/NaI): calculated for C13H19NO2S (MNa)+276.1034, found 276.1029; m.p. 69-70° C. (hexane).
Reaction SMILES: Cl[CH2:2][C:3]1[N:4]=[C:5]([NH:8][C:9]([NH:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([F:19])[CH:14]=2)=[O:10])[S:6][CH:7]=1.CN.ClC1C=C(C=CC=1Cl)[CH2:26][NH:27]C(NC1SC=C(CNC)N=1)=O>>[F:19][C:15]1[CH:14]=[C:13]([CH:18]=[CH:17][CH:16]=1)[CH2:12][NH:11][C:9]([NH:8][C:5]1[S:6][CH:7]=[C:3]([CH2:2][NH:27][CH3:26])[N:4]=1)=[O:10]
Reactant: CNCc1csc(NC(=O)NCc2ccc(Cl)c(Cl)c2)n1
Reactant: O=C(NCc1cccc(F)c1)Nc1nc(CCl)cs1
Agent: CN
Product: CNCc1csc(NC(=O)NCc2cccc(F)c2)n1

Procedure:
Prepared by reaction of Intermediate 4 with methylamine, following the procedure described for Intermediate 3.
Reaction SMILES: [C:1]([O:4][C@@H:5]1[C@@H:18]([O:19][C:20](=[O:22])[CH3:21])[C@H:17]([O:23][C:24](=[O:26])[CH3:25])[CH2:16][S:15][C@H:6]1[O:7][C:8]1[C:9](Cl)=[N:10][CH:11]=[CH:12][CH:13]=1)(=[O:3])[CH3:2].[C:27]1(B(O)O)[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[F-].[Cs+]>COCCOC>[C:1]([O:4][C@@H:5]1[C@@H:18]([O:19][C:20](=[O:22])[CH3:21])[C@H:17]([O:23][C:24](=[O:26])[CH3:25])[CH2:16][S:15][C@H:6]1[O:7][C:8]1[C:9]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[N:10][CH:11]=[CH:12][CH:13]=1)(=[O:3])[CH3:2]
Reactant: CC(=O)O[C@@H]1[C@@H](OC(C)=O)[C@H](OC(C)=O)CS[C@H]1Oc1cccnc1Cl
Reactant: OB(O)c1ccccc1
Agent: [Cs+]
Agent: [F-]
Solvent: COCCOC
Product: CC(=O)O[C@@H]1[C@@H](OC(C)=O)[C@H](OC(C)=O)CS[C@H]1Oc1cccnc1-c1ccccc1
Temperature: 120 °C
Yield: 90 %

Procedure:
0.1 g (0.24 mM) of 2-chloro-3-pyridinyl 2,3,4-tri-O-acetyl-5-thio-β-D-xylo-pyranoside, 30 ml of DME, 0.037 g (0.29 mM) of phenylboronic acid, 0.102 g (0.66 mM) of cesium fluoride and 0.021 g (0.024 mM) of [1,1′-bis(diphenyl-phosphino)ferrocene]dichloropalladium(II) dichloromethane are mixed. The mixture is heated for 2 hours at 120° C. under an inert atmosphere in a microwave oven. The reaction medium is then filtered on a Whatman filter, the material on the filter is rinsed with ethyl acetate and the filtrate is extracted. The pH is neutralized with ammonium chloride solution. The organic phase is dried over sodium sulfate and the product is concentrated under reduced pressure. It is purified by chromatography on a silica column (eluent: dichloromethane/ethyl acetate 99/1; v/v) to give the expected product in the form of a white powder with a yield of 90%.
Reaction SMILES: C([NH:3][C:4]1[S:5][C:6]([Cl:42])=[C:7]([C:9](=[N:32][O:33][CH2:34][C:35]([O:37][C:38]([CH3:41])([CH3:40])[CH3:39])=[O:36])[C:10]([NH:12][CH:13]2[C:30](=[O:31])[N:15]3[C:16]([C:27]([OH:29])=[O:28])=[C:17]([CH2:20][S:21][C:22]4[S:23][CH:24]=[N:25][N:26]=4)[CH2:18][S:19][C@H:14]23)=[O:11])[N:8]=1)=O.Cl.O.C(=O)(O)[O-].[Na+]>CO.C(OCC)(=O)C>[NH2:3][C:4]1[S:5][C:6]([Cl:42])=[C:7]([C:9](=[N:32][O:33][CH2:34][C:35]([O:37][C:38]([CH3:40])([CH3:39])[CH3:41])=[O:36])[C:10]([NH:12][CH:13]2[C:30](=[O:31])[N:15]3[C:16]([C:27]([OH:29])=[O:28])=[C:17]([CH2:20][S:21][C:22]4[S:23][CH:24]=[N:25][N:26]=4)[CH2:18][S:19][C@H:14]23)=[O:11])[N:8]=1
Reactant: CC(C)(C)OC(=O)CON=C(C(=O)NC1C(=O)N2C(C(=O)O)=C(CSc3nncs3)CS[C@H]12)c1nc(NC=O)sc1Cl
Agent: Cl
Agent: O=C([O-])O
Agent: [Na+]
Solvent: CO
Solvent: CCOC(C)=O
Solvent: O
Product: CC(C)(C)OC(=O)CON=C(C(=O)NC1C(=O)N2C(C(=O)O)=C(CSc3nncs3)CS[C@H]12)c1nc(N)sc1Cl
Temperature: 25 °C
Reaction time: 3 h
Yield: 75.9 %

Procedure:
A mixture of 7-[2-(2-formamido-5-chlorothiazol-4-yl)-2-tert-butoxycarbonylmethoxyiminoacetamido]-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (3.6 g) in methanol (36 ml) and conc. hydrochloric acid (1.1 g) was stirred for 3.0 hours at ambient temperature. The reaction mixture was added to water and ethyl acetate, and adjusted to pH 7.5 with a saturated aqueous solution of sodium bicarbonate. The aqueous layer was separated and adjusted to pH 3.0 with 10% aqueous hydrochloric acid, and then extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate, and evaporated to give 7-[2-(2-amino-5-chlorothiazol-4-yl)-2-tert-butoxycarbonylmethoxyiminoacetamido]-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (2.62 g).
Reaction SMILES: [CH3:1][C:2]1[CH2:3][C@H:4]([OH:11])[CH2:5][C:6]([CH3:10])([CH3:9])[C:7]=1[CH3:8].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.[CH:29]([O:31][CH2:32][CH3:33])=[CH2:30].C([O-])(O)=O.[Na+]>C(Cl)Cl>[CH2:29]([O:31][CH:32]([O:11][C@@H:4]1[CH2:5][C:6]([CH3:10])([CH3:9])[C:7]([CH3:8])=[C:2]([CH3:1])[CH2:3]1)[CH3:33])[CH3:30]
Reactant: CC1=C(C)C(C)(C)C[C@@H](O)C1
Reactant: C=COCC
Agent: Cc1ccc(S(=O)(=O)[O-])cc1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: ClCCl
Product: CCOC(C)O[C@H]1CC(C)=C(C)C(C)(C)C1
Temperature: 0 °C
Reaction time: 1 h

Procedure:
0.8 g (5.2 mmol) of (1S)-3,4,5,5-tetramethyl-3-cyclohexen-1-ol was dissolved under N2 in 5 ml of absolute methylene chloride, the solution was cooled to 0° C. and 260 mg (1.04 mmol) of pyridinium p-toluenesulfonate, and then 0.45 mg (6.2 mmol) of ethyl vinyl ether were added. The mixture was subsequently stirred at 0° C. for 1 h and then poured into a saturated aqueous NaHCO3 solution, the mixture was extracted with methylene chloride, and the extract was dried over MgSO4 and concentrated. The residue was purified by distillation to yield 1.1 g (corresponding to 97% of theory) of the abovementioned product.
Reaction SMILES: Cl.[CH2:2]([NH:6][C:7](=[O:43])[C@H:8]([CH3:42])[CH2:9][C@H:10]([OH:41])[C@@H:11]([NH:33]C(OC(C)(C)C)=O)[CH2:12][C:13]1([CH2:16][C:17]([N:19]2[C:28]3[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=3)[CH2:22][CH:21]([C:29]([NH:31][CH3:32])=[O:30])[CH2:20]2)=[O:18])[CH2:15][CH2:14]1)[CH2:3][CH2:4][CH3:5].C1(C)C=CC=CC=1>O1CCOCC1>[CH2:2]([NH:6][C:7](=[O:43])[C@H:8]([CH3:42])[CH2:9][C@H:10]([OH:41])[C@@H:11]([NH2:33])[CH2:12][C:13]1([CH2:16][C:17]([N:19]2[C:28]3[C:23](=[CH:24][CH:25]=[CH:26][CH:27]=3)[CH2:22][CH:21]([C:29]([NH:31][CH3:32])=[O:30])[CH2:20]2)=[O:18])[CH2:15][CH2:14]1)[CH2:3][CH2:4][CH3:5]
Reactant: CCCCNC(=O)[C@H](C)C[C@H](O)[C@H](CC1(CC(=O)N2CC(C(=O)NC)Cc3ccccc32)CC1)NC(=O)OC(C)(C)C
Agent: Cl
Solvent: Cc1ccccc1
Solvent: C1COCCO1
Product: CCCCNC(=O)[C@H](C)C[C@H](O)[C@@H](N)CC1(CC(=O)N2CC(C(=O)NC)Cc3ccccc32)CC1
Reaction time: 2 h

Procedure:
2 ml of 4N hydrochloric acid in dioxane are added to 116 mg of 5(S)-tert-butoxycarbonylamino-4(S)-hydroxy-6-[1-[3(R,S)-methylaminocarbonyl-1,2,3,4-tetrahydroquinolin-1-ylcarbonylmethyl]cyclopropyl]-2(R)-methyl-hexanoic acid (N-butyl)amide at 0° C. and the mixture is stirred for 2 h. 2 ml of toluene are added and the reaction mixture is concentrated. The oily residue is chromatographed over 10 g of silica gel (mobile phases K and L). This gives the title compound as a diastereomer mixture: Rf (P)=0.11; Rt (IV)=32.6 min; FAB-MS: (M+H)+ =487.
Reaction SMILES: CN.C[CH2:4][N:5](C(C)C)C(C)C.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.[CH2:36]([O:43][C:44]1[CH:45]=[C:46]2[C:52]([C:53]([OH:55])=O)=[C:51]([C:56]3[CH:61]=[CH:60][C:59]([F:62])=[CH:58][CH:57]=3)[O:50][C:47]2=[CH:48][N:49]=1)[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1>CN(C=O)C>[CH2:36]([O:43][C:44]1[CH:45]=[C:46]2[C:52]([C:53]([NH:5][CH3:4])=[O:55])=[C:51]([C:56]3[CH:57]=[CH:58][C:59]([F:62])=[CH:60][CH:61]=3)[O:50][C:47]2=[CH:48][N:49]=1)[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1
Reactant: CCN(C(C)C)C(C)C
Reactant: O=C(O)c1c(-c2ccc(F)cc2)oc2cnc(OCc3ccccc3)cc12
Agent: CN
Agent: CN(C)C(On1nnc2cccnc21)=[N+](C)C
Agent: F[P-](F)(F)(F)(F)F
Solvent: CN(C)C=O
Product: CNC(=O)c1c(-c2ccc(F)cc2)oc2cnc(OCc3ccccc3)cc12
Yield: 38.9 %

Procedure:
Methanamine (3.1 mL, 6.2 mmol, 2M in THF) was added to a stirring solution of DIEA (646 μL, 3.70 mmol), HATU (563 mg, 1.48 mmol), 5-(benzyloxy)-2-(4-fluorophenyl)furo[2,3-c]pyridine-3-carboxylic acid (448 mg, 1.23 mmol) in DMF (12 mL) at room temperature. The mixture concentrated then diluted with EtOAc and washed with sat NaCl. The organic phase was dried over Na2SO4, filtered and concentrated and was purified on silica gel (Biotage, EtOAc/hexanes gradient, fraction collection at λ=254 nm) to give 5-(benzyloxy)-2-(4-fluorophenyl)-N-methylfuro[2,3-c]pyridine-3-carboxamide (180 mg, 39% yield) consistent by LCMS and NMR. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.62 (1H, s), 8.37-8.45 (1H, m), 7.98-8.08 (2H, m), 7.29-7.50 (7H, m), 7.06 (1H, s), 5.42 (2H, s), 2.83 (3H, d, J=4.52 Hz). LC-MS retention time: 2.00 min; m/z (MH+): 377. LC data was recorded on a Shimadzu LC-10AS liquid chromatograph equipped with a Waters SunFire 5u C18 4.6×50 mm column using a SPD-10AV UV-Vis detector at a detector wave length of 220 nM. The elution conditions employed a flow rate of 5 ml/min, a gradient of 100% solvent A/0% solvent B to 0% solvent A/100% solvent B, a gradient time of 3 min, a hold time of 1 min, and an analysis time of 4 min where solvent A was 10% acetonitrile/90% H2O/0.1% trifluoroacetic acid and solvent B was 10% H2O/90% acetonitrile/0.1% trifluoroacetic acid. MS data was determined using a Micromass Platform for LC in electrospray mode.
Reaction SMILES: [N+:1]([C:4]1[CH:5]=[C:6]2[C:11](=[C:12]([C:14]([O:16][CH3:17])=[O:15])[CH:13]=1)[N:10]=[CH:9][NH:8][C:7]2=O)([O-:3])=[O:2].O=P(Cl)(Cl)Cl.CCN(C(C)C)C(C)C.[Cl:33][C:34]1[CH:41]=[CH:40][C:37]([CH2:38][NH2:39])=[CH:36][C:35]=1[C:42]([F:45])([F:44])[F:43]>ClCCCl>[Cl:33][C:34]1[CH:41]=[CH:40][C:37]([CH2:38][NH:39][C:7]2[C:6]3[C:11](=[C:12]([C:14]([O:16][CH3:17])=[O:15])[CH:13]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=3)[N:10]=[CH:9][N:8]=2)=[CH:36][C:35]=1[C:42]([F:43])([F:44])[F:45]
Reactant: NCc1ccc(Cl)c(C(F)(F)F)c1
Reactant: COC(=O)c1cc([N+](=O)[O-])cc2c(=O)[nH]cnc12
Solvent: O=P(Cl)(Cl)Cl
Solvent: ClCCCl
Solvent: CCN(C(C)C)C(C)C
Product: COC(=O)c1cc([N+](=O)[O-])cc2c(NCc3ccc(Cl)c(C(F)(F)F)c3)ncnc12
Temperature: 90 °C
Reaction time: 1 h
Yield: 46 %

Procedure:
To a solution of methyl 6-nitro-4-oxo-3,4-dihydroquinazoline-8-carboxylate (250 mg, 1.0 mmol) in 5 mL of anhydrous DCE, POCl3 (110 μL, 1.2 mmol, 1.2 equiv.) was added followed by DIPEA (870 μL, 5.0 mmol, 5.0 equiv.). The resulting mixture was stirred at 90° C. for 1 h. After cooling down to rt, 4-chloro-3-(trifluoromethyl)benzylamine (230 mg, 1.1 mmol, 1.1 equiv.) was added. The reaction mixture was stirred at 80° C. for 3 h. After work-up, the crude was purified by flash chromatography to yield the title compound in 46% yield. 1HNMR (in DMSO): 3.91 (s, 3H), 4.88 (d, J=5.9 Hz, 2H), 7.65-7.71 (m, 2H), 7.91 (s, 1H), 8.64 (s 1H), 8.68 (d, J=2.2 Hz, 1H), 9.49 (d, J=2.4 Hz, 1H), 9.70 (t, J=5.7 Hz, 1H). Mass: M+H+: 441.
Reaction SMILES: [CH3:1][C:2]1[NH:3][C:4]2[C:9]([CH:10]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2.C([Li])CCC.CC(C)([O-])C.[K+].[CH:22]1([CH2:28][C:29](=[O:43])[CH2:30][C:31]([C:34]2[CH:39]=[C:38]([F:40])[CH:37]=[CH:36][C:35]=2[O:41][CH3:42])([CH3:33])[CH3:32])[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1>C1COCC1>[CH:22]1([CH2:28][C:29]([CH2:1][C:2]2[NH:3][C:4]3[C:9]([CH:10]=2)=[CH:8][CH:7]=[CH:6][CH:5]=3)([OH:43])[CH2:30][C:31]([C:34]2[CH:39]=[C:38]([F:40])[CH:37]=[CH:36][C:35]=2[O:41][CH3:42])([CH3:33])[CH3:32])[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]1
Reactant: COc1ccc(F)cc1C(C)(C)CC(=O)CC1CCCCC1
Reactant: Cc1cc2ccccc2[nH]1
Agent: CC(C)(C)[O-]
Agent: [K+]
Agent: [Li]CCCC
Solvent: C1CCOC1
Product: COc1ccc(F)cc1C(C)(C)CC(O)(Cc1cc2ccccc2[nH]1)CC1CCCCC1
Temperature: -20 °C
Reaction time: 0.03 h
Yield: 66.5 %

Procedure:
To a solution of the 2-methylindole (65 mg) in THF (1 mL) stirred under argon cooled on dry ice/acetone was added n-butyl lithium (2 M in pentane, 0.8 mL). After 2 minutes, potassium tert-butoxide (1M in THF, 1 mL) was added and the mixture was allowed to warm to approximately −20° C. After 5 minutes, a precipitate was noted and the mixture was cooled to −70° C. 1-Cyclohexyl-4-(5-fluoro-2-methoxyphenyl)-4-methylpentan-2-one (Example 15) (100 mg) in THF (1 mL) was added dropwise and the mixture was stirred for 20 minutes at −70° C. The reaction was quenched with EtOH (0.5 mL). The mixture was diluted with EtOAc, washed with water, dried, filtered, and evaporated. Chromatography over silica gel (methylene chloride-hexanes (1:2)) gave the title compound as an oil (0.095 g).
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([C:14]([O:16][CH3:17])=[O:15])=[C:10]([CH3:18])[CH:9]=2)=[CH:4][CH:3]=1.Cl[C:20]1[S:21][C:22]2[CH:28]=[C:27]([F:29])[CH:26]=[CH:25][C:23]=2[N:24]=1.Cl.O1CCOCC1>C(O)CCC>[F:29][C:27]1[CH:26]=[CH:25][C:23]2[N:24]=[C:20]([NH:1][C:2]3[CH:3]=[CH:4][C:5]([C:8]4[CH:13]=[CH:12][C:11]([C:14]([O:16][CH3:17])=[O:15])=[C:10]([CH3:18])[CH:9]=4)=[CH:6][CH:7]=3)[S:21][C:22]=2[CH:28]=1
Reactant: COC(=O)c1ccc(-c2ccc(N)cc2)cc1C
Reactant: Fc1ccc2nc(Cl)sc2c1
Agent: Cl
Solvent: CCCCO
Solvent: C1COCCO1
Product: COC(=O)c1ccc(-c2ccc(Nc3nc4ccc(F)cc4s3)cc2)cc1C
Temperature: 65 °C
Yield: 58.2 %

Procedure:
As shown in Reaction Scheme 7, a mixture of methyl 4′-amino-3-methylbiphenyl-4-carboxylate (0.34 g, 1.40 mmol) and 2-chloro-6-fluoro-1,3-benzothiazole (0.26 g, 1.40 mmol) in n-butanol (4 mL) was heated to 60-70° C., and then 4N HCl in 1,4-dioxane (0.16 mL, 0.63 mmol) was added dropwise with stirring. The reaction mixture was heated at 90° C. for 18 h. Upon cooling to rt, the reaction mixture was concentrated in vacuo. The residue was triturated with ethanol and collected by filtration, yielding 0.32 g (58%) of the title compound as a pale yellow solid. LC/MS m/z 393.3 (MH+), retention time 4.02 min. 1H NMR (400 MHz, CD2Cl2) δ 2.62 (s, 3H), 3.95 (s, 3H), 7.05 (t, 1H), 7.39-7.60 (m, 4H), 7.65 (s, 4H), 7.96 (d, 1H).
Reaction SMILES: [CH2:1]([O:3][CH2:4][CH2:5][N:6]([C:15]1[CH:16]=[CH:17][CH:18]=[C:19]2[C:23]=1[NH:22][C:21]([C:24]1[S:25][C:26]([CH2:29]O)=[CH:27][N:28]=1)=[CH:20]2)[S:7]([C:10]1[S:11][CH:12]=[CH:13][CH:14]=1)(=[O:9])=[O:8])[CH3:2].O1CCCC1.S(Cl)([Cl:38])=O>CN(C)C=O.C(OCC)(=O)C.[Cl-].[Na+].O>[Cl:38][CH2:29][C:26]1[S:25][C:24]([C:21]2[NH:22][C:23]3[C:19]([CH:20]=2)=[CH:18][CH:17]=[CH:16][C:15]=3[N:6]([CH2:5][CH2:4][O:3][CH2:1][CH3:2])[S:7]([C:10]2[S:11][CH:12]=[CH:13][CH:14]=2)(=[O:9])=[O:8])=[N:28][CH:27]=1
Reactant: O=S(Cl)Cl
Reactant: CCOCCN(c1cccc2cc(-c3ncc(CO)s3)[nH]c12)S(=O)(=O)c1cccs1
Agent: [Cl-]
Agent: [Na+]
Solvent: CN(C)C=O
Solvent: CCOC(C)=O
Solvent: C1CCOC1
Product: CCOCCN(c1cccc2cc(-c3ncc(CCl)s3)[nH]c12)S(=O)(=O)c1cccs1
Temperature: 25 °C
Reaction time: 8 h
Yield: 93.3 %

Procedure:
To a mixture of N-(2-ethoxyethyl)-N-{2-[5-(hydroxymethyl)-1,3-thiazol-2-yl]-1H-indol-7-yl}thiophene-2-sulfonamide (1.00 g), N,N-dimethylformamide (1 drop) and tetrahydrofuran (15 mL) was added thionyl chloride (409 mg), and the mixture was stirred at room temperature overnight. The reaction mixture was diluted with ethyl acetate and saturated brine, and washed with saturated brine. The organic layer was dried over magnesium sulfate and filtrated. The filtrate was concentrated, and the obtained solid was washed with ether-hexane (1:1) to give the title compound (970 mg, yield 93%) as a pale-yellow solid.
Reaction SMILES: [CH2:1]=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].CCCCN1C=[N+](C)C=C1.[CH:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>N(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O.N(S(C(F)(F)F)(=O)=O)S(C(F)(F)F)(=O)=O.[Ni+2]>[CH2:1]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]
Reactant: C=CCCCCCC
Reactant: c1ccccc1
Agent: [Ni+2]
Agent: CCCCn1cc[n+](C)c1
Agent: O=S(=O)(NS(=O)(=O)C(F)(F)F)C(F)(F)F
Product: CCCCCCCCc1ccccc1
Temperature: 60 °C

Procedure:
Nickel(II) bis-triflimide (0.06 g, 0.1 mmol) was dissolved in [bmim] [NTf2] (1.0 g) in a round-bottomed flask equipped with a magnetic stirrer and reflux condenser. Benzene (3.90 g, 50 mmol) and oct-1-ene (1.12 g, 10 mmol) were added. The mixture was heated under reflux for 18 hours and was analysed by gas chromatographic analysis as in previous examples. The oct-1-ene peak disappeared and three isomers of octylbenzene were formed (70%, 20:26:54 2- to 3- to 4-isomer ratio) as well as octene dimer (30%). The less dense product phase was decanted from the ionic/catalyst phase and purified by Kugelrohr distillation. The ionic liquid and catalyst were prepared for reuse by heating at 60° C. under vacuum for 1 hour. The ionic liquid and catalyst were used for further reactions of benzene with oct-1-ene without loss of activity. This is an alkylation of benzene with an alkene using a metal bis-triflimide catalyst. Benzene and oct-1-ene react in the presence of 1% nickel(II) bis-triflimide in [bmim] [NTf2] to form three isomers of octyl benzene and a small amount of hexadecene (unknown isomeric distribution). This reaction shown below:
Reaction SMILES: [I:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[NH:8][N:9]=[CH:10][C:3]=12.Br[CH:12]([CH2:18][CH:19]1[CH2:24][CH2:23][O:22][CH2:21][CH2:20]1)[C:13]([O:15][CH2:16][CH3:17])=[O:14].O1CCC(C=CC(OCC)=O)CC1.C(=O)([O-])[O-].[K+].[K+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>CN(C)C=O>[I:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([CH:12]([CH2:18][CH:19]3[CH2:20][CH2:21][O:22][CH2:23][CH2:24]3)[C:13]([O:15][CH2:16][CH3:17])=[O:14])[N:9]=[CH:10][C:3]=12
Reactant: Ic1ccnc2[nH]ncc12
Reactant: CCOC(=O)C(Br)CC1CCOCC1
Agent: CCOC(=O)C=CC1CCOCC1
Agent: O=C(O)CC(O)(CC(=O)O)C(=O)O
Agent: O=C([O-])[O-]
Solvent: CN(C)C=O
Product: CCOC(=O)C(CC1CCOCC1)n1ncc2c(I)ccnc21
Yield: 53.1 %

Procedure:
A mixture of 4-iodo-1H-pyrazolo[3,4-b]pyridine (1.72 g), a 1:1 mixture (3.1 g) of ethyl 2-bromo-3-(tetrahydro-2H-pyran-4-yl)propanoate and ethyl 3-(tetrahydro-2H-pyran-4-yl)-2-propenoate, potassium carbonate (1.0 g) and N,N-dimethylformamide (15 mL) was stirred overnight at room temperature. To the reaction mixture was added aqueous citric acid solution, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and saturated brine, dried (MgSO4), and concentrated. The residue was subjected to silica gel column chromatography to give the title compound (1.6 g, yield 53%) as a colorless oil from the fraction eluted with ethyl acetate-hexane (35:75, volume ratio). MS: 430 (MH+).
Reaction SMILES: [N:1]1[CH:2]=[CH:3][N:4]2[C:9]=1[CH:8]=[CH:7][C:6]([O:10][C:11]1[CH:12]=[C:13]([CH:17]=[CH:18][CH:19]=1)[C:14]([OH:16])=O)=[N:5]2.[NH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.O.ON1C2C=CC=CC=2N=N1.Cl.CN(C)CCCN=C=NCC.C(N(CC)CC)C.[OH-].[Na+]>CN(C)C=O>[N:1]1[CH:2]=[CH:3][N:4]2[C:9]=1[CH:8]=[CH:7][C:6]([O:10][C:11]1[CH:12]=[C:13]([CH:17]=[CH:18][CH:19]=1)[C:14]([NH:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:16])=[N:5]2
Reactant: Nc1ccccc1
Reactant: O=C(O)c1cccc(Oc2ccc3nccn3n2)c1
Agent: CCN=C=NCCCN(C)C
Agent: Cl
Agent: On1nnc2ccccc21
Solvent: CCN(CC)CC
Solvent: O
Solvent: CN(C)C=O
Product: O=C(Nc1ccccc1)c1cccc(Oc2ccc3nccn3n2)c1
Temperature: 25 °C
Reaction time: 18 h
Yield: 74 %

Procedure:
To a mixture of 3-(imidazo[1,2-b]pyridazin-6-yloxy)benzoic acid (128 mg, 0.50 mmol), aniline (56 mg, 0.60 mmol), 1-hydroxybenzotriazole hydrate (92 mg, 0.60 mmol) and N,N-dimethylformamide (5 mL) were added 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (192 mg, 1.00 mmol) and triethylamine (0.209 mL, 1.50 mmol), and the mixture was stirred at room temperature for 18 hr. 1N Aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated brine and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/methanol=100/0→75/25) and precipitated from ethyl acetate to give the title compound (122 mg, 0.37 mmol, yield 74%) as a white solid.
Reaction SMILES: [CH2:1]([O:8][C:9](=[O:26])[CH:10]([NH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:11][C:12](N(OC)C)=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(C[AlH]CC(C)C)C>C1COCC1>[CH2:1]([O:8][C:9](=[O:26])[CH:10]([NH:18][C:19]([O:21][C:22]([CH3:24])([CH3:23])[CH3:25])=[O:20])[CH2:11][CH:12]=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: CON(C)C(=O)CC(NC(=O)OC(C)(C)C)C(=O)OCc1ccccc1
Agent: CC(C)C[AlH]CC(C)C
Solvent: C1CCOC1
Product: CC(C)(C)OC(=O)NC(CC=O)C(=O)OCc1ccccc1
Reaction time: 1.5 h

Procedure:
To 2-tert-butoxycarbonylamino-N-methoxy-N-methyl succinamic acid benzyl ester (0.50 g, 1.36 mmol) in THF (5 mL) at −78° C. was added DIBAL-H (0.233 g, 1.67 mmol) dropwise. The mixture was stirred for 1.5 h and monitored by TLC. When completed the reaction was quenched with 5 mL of saturated solution of Rochell salt (KNaC4H4O6.4H2O) (potassium sodium tartrate) and extracted with EtOAc (2×10 mL). The organic layer was washed with H2O, brine, dried over Na2SO4, filtered and concentrated in vacuo to give the title compound in quantitative yield (0.40 g).