Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [C:1]1([SH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[NH:8]([C:13]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:14])[CH2:9][C:10]([OH:12])=[O:11]>ClCCl>[C:1]1([S:7][O:12][C:10](=[O:11])[CH2:9][NH:8][C:13]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[O:14])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: O=C(O)CNC(=O)OCc1ccccc1
Reactant: Sc1ccccc1
Solvent: ClCCl
Product: O=C(CNC(=O)OCc1ccccc1)OSc1ccccc1
Yield: 62 %

Procedure:
Using thiophenol and Z-Gly.OH, Example 78 was repeated; except that dichloromethane was used in place of ethyl acetate as the extraction solvent, to obtain N-benzyloxycarbonyl-glycine-phenythio ester (hereinafter represented by ##STR12## in a yield of 62%.
Reaction SMILES: [NH:1]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:4](=[O:5])[C:2]1=[O:3].CC(C)([O-])C.[K+].[Br:18][CH2:19][CH2:20][CH2:21][CH2:22]Br>CN(C)C=O>[Br:18][CH2:19][CH2:20][CH2:21][CH2:22][N:1]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:4](=[O:5])[C:2]1=[O:3]
Reactant: O=C1Nc2ccccc2C1=O
Reactant: BrCCCCBr
Agent: CC(C)(C)[O-]
Agent: [K+]
Solvent: CN(C)C=O
Product: O=C1C(=O)N(CCCCBr)c2ccccc21
Temperature: 5 °C
Reaction time: 0.17 h
Yield: 53.4 %

Procedure:
To a solution of isatin (7.35 g) in N,N-dimethylformamide (70 ml) was added potassium tert-butoxide (6.98 g) under cooling at 5° C., and the reaction mixture was stirred for 10 minutes at the same temperature. To the mixture was added dropwise a solution of 1,4-dibromobutane (54 g) in N,N-dimethylformamide (25 ml), and stirred for an hour at 18° C. The reaction mixture was poured into ice-water, and extracted with chloroform. The extracts were combined, washed with water and evaporated. After addition of n-hexane (200 ml) to the residue, the solvent was decanted and then to the residue was added chloroform (20 ml). The mixture was filtered to remove insoluble substances and the filtrate was subjected to column chromatography on silica gel (50 g), eluted with chloroform. The fractions containing the object compound were collected, and concentrated to give dark red oil of 1-(4-bromobutyl)isatin (7.52 g).
Reaction SMILES: [CH3:1][C:2]1[CH:29]=[C:28]2[C:5]([CH2:6][CH2:7][C:8]3[C:9]2=[N:10][O:11][C:12]=3[C:13]2[C:17]([C:18]([F:21])([F:20])[F:19])=[C:16]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[O:15][N:14]=2)=[CH:4][C:3]=1[CH:30]=C.[O:32]=[O+][O-].C(N(CC)CC)C>ClCCl>[CH3:1][C:2]1[CH:29]=[C:28]2[C:5]([CH2:6][CH2:7][C:8]3[C:9]2=[N:10][O:11][C:12]=3[C:13]2[C:17]([C:18]([F:21])([F:19])[F:20])=[C:16]([C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)[O:15][N:14]=2)=[CH:4][C:3]=1[CH:30]=[O:32]
Reactant: C=Cc1cc2c(cc1C)-c1noc(-c3noc(-c4ccccc4)c3C(F)(F)F)c1CC2
Reactant: O=[O+][O-]
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: Cc1cc2c(cc1C=O)CCc1c-2noc1-c1noc(-c2ccccc2)c1C(F)(F)F
Temperature: 25 °C
Reaction time: 0.08 h

Procedure:
To a solution of 8-methyl-3-(5-phenyl-4-(trifluoromethyl)isoxazol-3-yl)-7-vinyl-4,5-dihydronaphtho[1,2-c]isoxazole (Preparation 64E, 0.058 g, 0.137 mmol) in dichloromethane (10 mL) at −78° C. was passed ozone from an ozone generator until the solution turned a deep blue. The reaction mixture then was purged with oxygen until the blue color disappeared, then with nitrogen for five minutes. The reaction mixture was allowed to warm to room temperature and triethylamine (0.019 mL, 0.137 mmol) was added. The reaction mixture was stirred at room temperature for fifteen minutes and then concentrated under vacuum to give 8-methyl-3-(5-phenyl-4-(trifluoromethyl)isoxazol-3-yl)-4,5-dihydronaphtho[1,2-c]isoxazole-7-carbaldehyde as a tan solid (0.043, 0.101 mmol, 74%). The product had an HPLC ret. time=3.43 min (condition B). LC/MS M+1=425.10.
Reaction SMILES: [NH2:1][C:2](=[S:17])[CH2:3][N:4]1[C:8]([CH3:9])=[C:7]([C:10]([O:12]C(C)(C)C)=[O:11])[CH:6]=[N:5]1.Br[CH2:19][C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([C:28]([F:31])([F:30])[F:29])[CH:23]=1)=O>>[CH3:9][C:8]1[N:4]([CH2:3][C:2]2[S:17][CH:19]=[C:20]([C:22]3[CH:27]=[CH:26][CH:25]=[C:24]([C:28]([F:29])([F:30])[F:31])[CH:23]=3)[N:1]=2)[N:5]=[CH:6][C:7]=1[C:10]([OH:12])=[O:11]
Reactant: Cc1c(C(=O)OC(C)(C)C)cnn1CC(N)=S
Reactant: O=C(CBr)c1cccc(C(F)(F)F)c1
Product: Cc1c(C(=O)O)cnn1Cc1nc(-c2cccc(C(F)(F)F)c2)cs1
Yield: 81.7 %

Procedure:
A reaction similar to Example 1c was performed using the compound (200 mg, 0.783 mmol) obtained in Example 11b and 2-bromo-1-[3-(trifluoromethyl)phenyl]ethanone (209 mg, 0.783 mmol). As a result, the title compound (235 mg, 81%) wherein tert-butyl ester was hydrolyzed by hydrobromic acid produced under the reaction conditions was obtained as colorless crystals.
Reaction SMILES: CO[C:3]1[C:4](=[O:22])[C:5]([N:10]([S:12]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)(=[O:14])=[O:13])[CH3:11])=[CH:6][CH:7]=[CH:8][CH:9]=1.[NH3:23]>CO>[NH2:23][C:3]1[C:4](=[O:22])[C:5]([N:10]([S:12]([C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)(=[O:14])=[O:13])[CH3:11])=[CH:6][CH:7]=[CH:8][CH:9]=1
Reactant: N
Reactant: COc1ccccc(N(C)S(=O)(=O)c2ccc(C)cc2)c1=O
Solvent: CO
Product: Cc1ccc(S(=O)(=O)N(C)c2ccccc(N)c2=O)cc1
Temperature: 80 °C

Procedure:
A solution at -25° C of 2-methoxy-7-[N-[(4-methylphenyl)sulfonyl]-N-methylamino]-2,4,6cycloheptatrien-1-one (described above, 4.0 g) in methanol (40 ml) is saturated with ammonia gas and heated in a pressure bottle at 80° C for 4 hours. The solution is cooled to -70° C, the bottle is opened and the solvent is evaporated to yield 2-amino-7-[N-[(4-methylphenyl)sulfonyl]-N-methylamino]-2,4,6-cycloheptatrien-1-one, mp 221°-222° C.
Reaction SMILES: C([O:4][C@@H:5]1[C@@H:10]([O:11]C(=O)C)[C@H:9]([O:15]C(=O)C)[C@@H:8]([CH2:19][O:20]C(=O)C)[O:7][C@H:6]1[C:24]1[CH:29]=[CH:28][C:27]([Cl:30])=[C:26]([CH2:31][C:32]2[S:33][C:34](Br)=[CH:35][CH:36]=2)[CH:25]=1)(=O)C.C([Sn](CCCC)(CCCC)[C:43]1[CH:48]=[CH:47][CH:46]=[C:45]([O:49][CH3:50])[N:44]=1)CCC>>[C@@H:6]1([C:24]2[CH:29]=[CH:28][C:27]([Cl:30])=[C:26]([CH2:31][C:32]3[S:33][C:34]([C:43]4[CH:48]=[CH:47][CH:46]=[C:45]([O:49][CH3:50])[N:44]=4)=[CH:35][CH:36]=3)[CH:25]=2)[O:7][C@H:8]([CH2:19][OH:20])[C@@H:9]([OH:15])[C@H:10]([OH:11])[C@H:5]1[OH:4]
Reactant: CCCC[Sn](CCCC)(CCCC)c1cccc(OC)n1
Reactant: CC(=O)OC[C@H]1O[C@@H](c2ccc(Cl)c(Cc3ccc(Br)s3)c2)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
Product: COc1cccc(-c2ccc(Cc3cc([C@@H]4O[C@H](CO)[C@@H](O)[C@H](O)[C@H]4O)ccc3Cl)s2)n1

Procedure:
1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-chlorobenzene 71 obtained in Example 128-(4) and tri-n-butyl(6-methoxy-2-pyridyl)tin (see Gros, Philippe; Fort, Yves. Synthesis (1999), 754-756) were treated in a manner similar to Example 128-(5) and (6) to give the target compound. APCI-Mass m/Z 478/480 (M+H).
Reaction SMILES: [Mg].[CH3:2][SiH:3]([CH3:5])Cl.Br[C:7]1[CH:16]=[CH:15][C:10]([O:11][SiH:12]([CH3:14])[CH3:13])=[CH:9][CH:8]=1>O1CCCC1>[CH3:2][SiH:3]([CH3:5])[C:7]1[CH:16]=[CH:15][C:10]([O:11][SiH:12]([CH3:14])[CH3:13])=[CH:9][CH:8]=1
Reactant: C[SiH](C)Oc1ccc(Br)cc1
Reactant: C[SiH](C)Cl
Agent: [Mg]
Solvent: C1CCOC1
Product: C[SiH](C)Oc1ccc([SiH](C)C)cc1

Procedure:
To a three-necked 2-1 flask containing 37.0 g (1.52 mol) of magnesium, 94.0 g (1 mol) of dimethylchlorosilane and 100 ml of freshly-distilled tetrahydrofuran was added slowly and under nitrogen a solution of 328.0 g (1.42 mol) of 4-bromophenoxydimethylsilane and 94.0 g (1 mol) of dimethylchlorosilane. During the addition, the reaction temperature was kept at 40°-50° C. After the addition was complete, the reaction mixture was refluxed and part of the tetrahydrofuran was removed by distillation. After cooling, the inorganic salt was precipitated by petroleum ether (b.p. 30°-60° C.) and filtered. The filtrate was concentrated on a rotary evaporator and then vacuum distilled. The expected compound (234.0 g, 78.5%) distilled at 85°-95° C./3.5 mm.
Reaction SMILES: [H-].[Na+].[F:3][C:4]1[C:5](=[O:38])[NH:6][C:7](=[O:37])[N:8]([CH:36]=1)[C@@H:9]1[O:35][C@H:13]([CH2:14][O:15]C(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[C@@H:11]([OH:12])[CH2:10]1.Cl[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][N:41]=1>CS(C)=O>[F:3][C:4]1[C:5](=[O:38])[NH:6][C:7](=[O:37])[N:8]([CH:36]=1)[C@@H:9]1[O:35][C@H:13]([CH2:14][OH:15])[C@@H:11]([O:12][C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][N:41]=2)[CH2:10]1
Reactant: O=c1[nH]c(=O)n([C@H]2C[C@H](O)[C@@H](COC(c3ccccc3)(c3ccccc3)c3ccccc3)O2)cc1F
Reactant: Clc1ccccn1
Agent: [H-]
Agent: [Na+]
Solvent: CS(C)=O
Product: O=c1[nH]c(=O)n([C@H]2C[C@H](Oc3ccccn3)[C@@H](CO)O2)cc1F
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 80 %

Procedure:
A 0.30 g quantity of sodium hydride (60%, dispersion in mineral oil) was added to a solution of 2.00 g of 2'-deoxy-5-fluoro-5'-O-trityluridine in 10 ml of dimethyl sulfoxide. The mixture was stirred at room temperature for 30 minutes. To the mixture was added 0.46 ml of 2-chloropyridine. Then the mixture was stirred at 80° C. for 3 hours. The solvent was distilled off and the residue was dissolved in 50 ml of ethyl acetate and 30 ml of water. The solution was made into a weak acidic solution by addition of 6N-hydrochloric acid. The ethyl acetate layer was separated, washed with water and concentrated. The residue was dissolved with heating in 20 ml of 80% acetic acid. The solution was left to stand at 80° C. for 1 hour and concentrated. The residue was dissolved in 50 ml of ethyl acetate, and the solution was washed with water, dried on anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography using 1% methanol-chloroform as an eluent, giving 1.06 g of 2'-deoxy-5-fluoro-3'-O-(2-pyridyl)uridine in a yield of 80%.
Reaction SMILES: [Br:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[C:4]([N+:9]([O-])=O)[C:3]=1[OH:12].[H][H]>C(OCC)(=O)C.[Ni]>[NH2:9][C:4]1[C:3]([OH:12])=[C:2]([Br:1])[CH:7]=[C:6]([Cl:8])[CH:5]=1
Reactant: [H][H]
Reactant: O=[N+]([O-])c1cc(Cl)cc(Br)c1O
Agent: [Ni]
Solvent: CCOC(C)=O
Product: Nc1cc(Cl)cc(Br)c1O
Yield: 99 %

Procedure:
A solution of 2-bromo-4-chloro-6-nitro-phenol (16.27 g, 64.4 mmol) in ethyl acetate (160 ml) was hydrogenated, at room temperature, with Raney-nickel (6 g). After hydrogen uptake (approx. 4.8 l) was complete, the nickel was removed by filtration and the filtrate evaporated in-vacuo to give 14.19 g (99.0%) of the title compound which was suitable for the next step.
Reaction SMILES: [Cl:1][CH2:2][C:3](Cl)=[O:4].[CH3:6][O:7][C:8]([C:10]1[CH:11]=[C:12]([CH3:29])[C:13]2[O:19][C:18]3[C:20]([Cl:25])=[CH:21][C:22]([NH2:24])=[CH:23][C:17]=3[CH2:16][S:15](=[O:27])(=[O:26])[C:14]=2[CH:28]=1)=[O:9].N1C=CC=CC=1>ClCCl>[CH3:6][O:7][C:8]([C:10]1[CH:11]=[C:12]([CH3:29])[C:13]2[O:19][C:18]3[C:20]([Cl:25])=[CH:21][C:22]([NH:24][C:3](=[O:4])[CH2:2][Cl:1])=[CH:23][C:17]=3[CH2:16][S:15](=[O:27])(=[O:26])[C:14]=2[CH:28]=1)=[O:9]
Reactant: O=C(Cl)CCl
Reactant: COC(=O)c1cc(C)c2c(c1)S(=O)(=O)Cc1cc(N)cc(Cl)c1O2
Solvent: c1ccncc1
Solvent: ClCCl
Product: COC(=O)c1cc(C)c2c(c1)S(=O)(=O)Cc1cc(NC(=O)CCl)cc(Cl)c1O2
Reaction time: 2 h

Procedure:
Chloroacetylchloride (3.3 mL, 40.8 mmol) was added to the solution of compound of Example 1 (5 g, 13.6 mmol) in dichloromethane (100 mL) at 20° C. Pyridine (6.6 mL, 81.6 mmol) was added and the reaction mixture was stirred for 2 h. The solvent was removed under vacuum and water (200 mL) was added. The solid obtained was filtered, washed with water and purified by stirring in ethyl acetate (200 mL) at reflux condition for 30 min. The solid was filtered and dried to obtain the title compound. Yield: 4.86 g (80.1%); mp 292-293° C.; 1H NMR (DMSO-d6, 300 MHz): δ 2.64 (s, 3H, CH3), 3.86 (s, 3H, OCH3), 4.27 (s, 2H, CH2), 5.34 (s, 2H, CH2), 7.67 (s, 1H, Ar), 7.88 (s, 1H, Ar), 8.11 (s, 1H, Ar), 8.15 (s, 1H, Ar), 10.70 (s, 1H, NH); MS: m/e (ES+) 445 (M+1); analysis: C18H15Cl2NO6S requires C, 48.66; H, 3.40; N, 3.15; Cl, 15.96; S, 7.22. found: C, 48.09; H, 3.37; N, 3.38; Cl, 16.37; S, 7.72%.
Reaction SMILES: [SH:1][C:2]1[NH:3][C:4]2[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:5]=2[N:6]=1.O[CH2:13][C:14]1[N:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:17]2=[N:16][CH:15]=1.C(O)(=O)C.C(=O)([O-])[O-].[K+].[K+]>Br.O>[N:16]1[CH:15]=[C:14]([CH2:13][S:1][C:2]2[NH:6][C:5]3[CH:7]=[CH:8][C:9]([CH3:11])=[CH:10][C:4]=3[N:3]=2)[N:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=12
Reactant: Cc1ccc2nc(S)[nH]c2c1
Reactant: OCc1cnc2ccccn12
Agent: Br
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC(=O)O
Solvent: O
Product: Cc1ccc2[nH]c(SCc3cnc4ccccn34)nc2c1
Temperature: 25 °C

Procedure:
A mixture of 903 mg (5.5 mmole) of 2-mercapto-5-methylbenzimidazole and 805 mg (5.4 mmole) of 3-hydroxymethylimidazo[1,2-a]pyridine (prepared as in Example 1) was dissolved in 10 ml of 48% aqueous hydrobromic acid and 10 ml of acetic acid and heated to reflux. After being cooled to room temperature, the mixture was poured into water and made alkaline with potassium carbonate. The oil that separated was extracted into dichloromethane, washed with water, dried over magnesium sulfate, filtered, and concentrated to an oil that crystallized on standing. The solid was collected by filtration, washed with diethyl ether, and air dried to yield the title compound as 610 mg of analytically pure solid. Structure assignment was supported by the nmr and infrared spectra and by elemental analysis.
Reaction SMILES: CON(C)[C:4](=[O:21])/[CH:5]=[CH:6]/[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[C:9]([O:15][CH:16]2[CH2:20][CH2:19][CH2:18][CH2:17]2)[CH:8]=1.[CH3:23][CH2:24][Mg]Br>C1COCC1.CCOCC>[CH:16]1([O:15][C:9]2[CH:8]=[C:7](/[CH:6]=[CH:5]/[C:4](=[O:21])[CH2:23][CH3:24])[CH:12]=[CH:11][C:10]=2[O:13][CH3:14])[CH2:17][CH2:18][CH2:19][CH2:20]1
Reactant: COc1ccc(/C=C/C(=O)N(C)OC)cc1OC1CCCC1
Reactant: CC[Mg]Br
Solvent: C1CCOC1
Solvent: CCOCC
Product: CCC(=O)/C=C/c1ccc(OC)c(OC2CCCC2)c1
Reaction time: 0.5 h
Yield: 34 %

Procedure:
To a solution of (E)-N-methoxy-N-methyl-3-(3-cyclopentoxy-4-methoxyphenyl)-prop-2-enamide (1.33 g, 4.36 mmol) in 8.0 mL of THF cooled to 0° C. was added CH3CH2MgBr (9 mL of 1.0M THF solution). The resulting solution was stirred for 30 min, diluted with ether and transferred to a separatory funnel. After washing with H2O, 1M H3PO4, and brine, the organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure. Silica gel chromatography (4:1, hexanes:ethyl acetate) provided (E)-5-(3-cyclopentoxy-4-methoxyphenyl)-pent-4-en-3-one as a white solid (400 mg, 34%). 1H-NMR (300 MHz): δ 1.17 (t, 3, J=7.6), 2.69 (q, 2, J=7.3), 3.89 (s, 3), 6.59 (d, 1, J=16), 7.50 (d, 1, J=16). Anal. Calcd for C17H22O3 : C, 74.42; H, 8.08. Found: C, 74.52; H, 8.13.
Reaction SMILES: [N:1]([O-])=O.[Na+].[Cl:5][C:6]1[N:11]=[C:10]([NH:12][CH2:13][C:14]2[S:15][C:16]3[CH:21]=[CH:20][N:19]=[CH:18][C:17]=3[N:22]=2)[C:9]([NH2:23])=[CH:8][CH:7]=1.[OH-].[Na+]>O.CC(O)=O>[Cl:5][C:6]1[N:11]=[C:10]2[N:12]([CH2:13][C:14]3[S:15][C:16]4[CH:21]=[CH:20][N:19]=[CH:18][C:17]=4[N:22]=3)[N:1]=[N:23][C:9]2=[CH:8][CH:7]=1
Reactant: Nc1ccc(Cl)nc1NCc1nc2cnccc2s1
Reactant: O=N[O-]
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: CC(=O)O
Product: Clc1ccc2nnn(Cc3nc4cnccc4s3)c2n1
Temperature: 0 °C
Reaction time: 1 h

Procedure:
A solution of NaNO2 (42.5 mg, 0.62 mmol) in H2O (0.5 mL) was added dropwise to a solution of 6-chloro-N2-(thiazolo[4,5-c]pyridin-2-ylmethyl)pyridine-2,3-diamine (90 mg, 0.31 mmol) in AcOH (1 mL) and H2O (1 mL) at 0° C. The reaction solution was stirred at 0° C. for 1 h, then basified with 30% aqueous NaOH to pH ˜9. The resulting precipitate was collected by filtration to afford the title compound. MS (m/z): 303 (M+1)+.
Reaction SMILES: [CH2:1]([C@H:7]1[C@H:10]([CH2:11][C@H:12]([OH:17])[CH2:13][CH2:14][CH:15]=[CH2:16])[O:9][C:8]1=[O:18])[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6].[CH:19]([NH:21][C@H:22]([C:27]([OH:29])=O)[CH2:23][CH:24]([CH3:26])[CH3:25])=[O:20]>>[CH2:1]([C@@H:7]1[C:8](=[O:18])[O:9][C@H:10]1[CH2:11][C@H:12]([O:17][C:27](=[O:29])[C@@H:22]([CH2:23][CH:24]([CH3:25])[CH3:26])[NH:21][CH:19]=[O:20])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:8][CH2:7][CH2:1][CH2:2][CH2:3][CH2:4][CH3:5])[CH2:2][CH2:3][CH2:4][CH2:5][CH3:6]
Reactant: CC(C)C[C@H](NC=O)C(=O)O
Reactant: C=CCC[C@@H](O)C[C@@H]1OC(=O)[C@H]1CCCCCC
Product: CCCCCCCCCCC[C@H](C[C@@H]1OC(=O)[C@H]1CCCCCC)OC(=O)[C@@H](CC(C)C)NC=O

Procedure:
by esterifying (S)-3-hexyl-(S)-4-[(R)-2-hydroxy-5-hexenyl)-2-oxetanone with N-formyl-L-leucine there was obtained
Reaction SMILES: [CH3:1][O:2][C:3](=[O:25])[CH2:4][C:5]1[CH:6]=[C:7]([C:13]2[CH:18]=[CH:17][C:16]([C:19]([F:22])([F:21])[F:20])=[CH:15][C:14]=2[CH:23]=O)[C:8]([O:11][CH3:12])=[CH:9][CH:10]=1.[CH:26]1([NH2:29])[CH2:28][CH2:27]1>>[CH3:1][O:2][C:3](=[O:25])[CH2:4][C:5]1[CH:6]=[C:7]([C:13]2[CH:18]=[CH:17][C:16]([C:19]([F:22])([F:21])[F:20])=[CH:15][C:14]=2[CH2:23][NH:29][CH:26]2[CH2:28][CH2:27]2)[C:8]([O:11][CH3:12])=[CH:9][CH:10]=1
Reactant: COC(=O)Cc1ccc(OC)c(-c2ccc(C(F)(F)F)cc2C=O)c1
Reactant: NC1CC1
Product: COC(=O)Cc1ccc(OC)c(-c2ccc(C(F)(F)F)cc2CNC2CC2)c1

Procedure:
Prepared according to the procedure described in Example 1, Step 5, using the following starting materials: (2′-formyl-6-methoxy-4′-trifluoromethyl-biphenyl-3-yl)-acetic acid methyl ester and cyclopropylamine.
Reaction SMILES: [Br:1][C:2]1[CH:3]=[C:4]([S:8][CH3:9])[CH:5]=[CH:6][CH:7]=1.C1C=C(Cl)C=C(C(OO)=[O:18])C=1>CCOC(C)=O.O>[CH3:9][S:8]([C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([Br:1])[CH:3]=1)=[O:18]
Reactant: CSc1cccc(Br)c1
Reactant: O=C(OO)c1cccc(Cl)c1
Solvent: O
Solvent: CCOC(C)=O
Product: CS(=O)c1cccc(Br)c1
Temperature: 25 °C
Reaction time: 4 h
Yield: 69393.7 %

Procedure:
A mixture of 3-bromothioanisole (4.9687 g, 0.0245 mmol) and MCPBA (5.066 g, %) was stirred at room temperature. After 4 h, extractive EtOAc/H2O workup followed by flash chromatography (EtOAc/Hexanes, 50:50) provided the title compound (3.725 g, 69%) as an oil. 1H NMR (DMSO, 400 MHz): 7.80 (br s, 1H), 7.61 (d, J=8.01 Hz, 1H), 7.53 (d, J=8.01 Hz, 1H), 7.39 (t, J=8.01 Hz, 1H), 2.72 (s, 3H).