Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: C(Cl)(=O)C(Cl)=O.CS(C)=O.[N:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[N:17]1[C:21]([C:22]([F:25])([F:24])[F:23])=[C:20]([C:26]2[O:30][N:29]=[C:28]([C:31]3[CH:36]=[CH:35][C:34]([CH2:37][OH:38])=[CH:33][CH:32]=3)[N:27]=2)[CH:19]=[N:18]1.CCN(C(C)C)C(C)C>C(Cl)Cl>[N:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[N:17]1[C:21]([C:22]([F:23])([F:24])[F:25])=[C:20]([C:26]2[O:30][N:29]=[C:28]([C:31]3[CH:32]=[CH:33][C:34]([CH:37]=[O:38])=[CH:35][CH:36]=3)[N:27]=2)[CH:19]=[N:18]1
Reactant: OCc1ccc(-c2noc(-c3cnn(-c4ccccn4)c3C(F)(F)F)n2)cc1
Agent: O=C(Cl)C(=O)Cl
Solvent: ClCCl
Solvent: CS(C)=O
Solvent: CCN(C(C)C)C(C)C
Product: O=Cc1ccc(-c2noc(-c3cnn(-c4ccccn4)c3C(F)(F)F)n2)cc1
Temperature: -78 °C
Reaction time: 0.17 h
Yield: 67.4 %

Procedure:
300 mL of DCM was cooled to −78° C., then oxalyl chloride (0.475 mL, 5.42 mmol) was added and the mixture was stirred at −78° C. for 10 min. DMSO (0.586 mL, 8.26 mmol) was added and the mixture was stirred at −78° C. for 15 min. A solution of (4-(5-(1-(pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazol-4-yl)-1,2,4-oxadiazol-3-yl)phenyl)methanol (1 g, 2.58 mmol) in 60 mL of DCM was added dropwise over 10 minutes into the reaction mixture, with the SM flask being rinsed with another 10 mL of DCM which was also added into the reaction dropwise. The reaction was kept at −78° C. for 40 min, then Hunig's Base (3.61 mL, 20.66 mmol) was added over 10 minutes. Stirring at −78° C. continued for 10 min, then the dry ice bath was removed and the reaction flask gradually warmed to room temperature. A 0.5 N KHSO4 solution (70 mL) was added and the mixture was extracted twice with DCM (50 mL). The organics were combined, dried with Na2SO4, and concentrated. Diethyl ether (100 mL) was added to the product, with the mixture being stirred overnight, then filtered and the solids washed with diethyl ether to afford 4-(5-(1-(pyridin-2-yl)-5-(trifluoromethyl)-1H-pyrazol-4-yl)-1,2,4-oxadiazol-3-yl)benzaldehyde (700 mg, 1.74 mmol). The compound had an HPLC retention time=3.69 min.−Column: CHROMOLITH® SpeedROD 4.6×50 mm (4 min.); Solvent A=10% MeOH, 90% H2O, 0.2% H3PO4; Solvent B=90% MeOH, 10% H2O, 0.2% H3PO4. LC/MS M+1=386.01. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.69 (ddd, J=0.8 Hz, 5.0 Hz, 7.4 Hz, 1H), 7.90 (d, J=8.0 Hz, 1H), 8.15 (d, J=8.3 Hz, 2H), 8.20 (dt, J=1.9 Hz, 7.7 Hz, 1H), 8.32 (d, J=8.3 Hz, 2H), 8.67 (dd, J=1.9 Hz, 4.7 Hz, 1H), 8.76 (s, 1H), 10.13 (s, 1H)
Reaction SMILES: [O:1]=[C:2]1[CH2:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([C:11](OC)=[O:12])[CH:8]=2)[NH:3]1.O1CCCC1.C(O)C.[BH4-].[Li+]>C(O)C>[OH:12][CH2:11][C:7]1[CH:8]=[C:9]2[C:4](=[CH:5][CH:6]=1)[NH:3][C:2](=[O:1])[CH2:10]2
Reactant: COC(=O)c1ccc2c(c1)CC(=O)N2
Agent: [BH4-]
Agent: [Li+]
Solvent: C1CCOC1
Solvent: CCO
Product: O=C1Cc2cc(CO)ccc2N1
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 33 %

Procedure:
To an ice-cooled mixture of methyl 2-oxoindoline-5-carboxylate (0.5 gram, 2.6 mmol) in a tetrahydrofuran/ethanol mixture (15:0.3 mL) was added lithium borohydride (115 mg, 5.2 mmol) in one portion. After 30 min, another portion of lithium borohydride (100 mg, 4.5 mmol) was added and the reaction solution was stirred for 4 h at room temperature. A third portion of lithium borohydride (200 mg, 9.2 mmol) and ethanol (0.3 mL) were added and the reaction solution was stirred for 14 h at room temperature. The reaction was quenched with water (10 mL) and an aqueous saturated ammonium chloride solution (30 mL) and extracted with ethyl acetate. The combined organic phases were dried (Na2SO4) and evaporated in vacuo. The crude product was purified on a silica gel column using methylene chloride/methanol, (10:1) as the eluent to give 140 mg (33% yield) of the title compound: 1H NMR (DMSO-d6, 300 MHz) δ 10.3 (br s, 1 H), 7.14 (s, 1 H), 7.09 (d, J=8 Hz, 1 H), 6.74 (d, J=8 Hz, 1 H), 5.03 (t, J=6 Hz, 1 H), 4.41 (7, J=6 Hz, 2 H), 3.44 (s, 2 H).
Reaction SMILES: [F:1][C:2]1[CH:3]=[C:4]([OH:27])[CH:5]=[CH:6][C:7]=1[C:8]1[N:13]=[C:12]2[NH:14][N:15]=[C:16]([CH3:17])[C:11]2=[C:10]([CH2:18][N:19]2[CH2:25][CH2:24][CH2:23][NH:22][CH:21]([CH3:26])[CH2:20]2)[CH:9]=1.C1COCC1.[CH2:33]([N:35]=[C:36]=[O:37])[CH3:34].CCN(C(C)C)C(C)C>O>[CH2:33]([NH:35][C:36]([N:22]1[CH2:23][CH2:24][CH2:25][N:19]([CH2:18][C:10]2[CH:9]=[C:8]([C:7]3[CH:6]=[CH:5][C:4]([OH:27])=[CH:3][C:2]=3[F:1])[N:13]=[C:12]3[NH:14][N:15]=[C:16]([CH3:17])[C:11]=23)[CH2:20][CH:21]1[CH3:26])=[O:37])[CH3:34]
Reactant: CCN=C=O
Reactant: Cc1n[nH]c2nc(-c3ccc(O)cc3F)cc(CN3CCCNC(C)C3)c12
Solvent: C1CCOC1
Solvent: CCN(C(C)C)C(C)C
Solvent: O
Product: CCNC(=O)N1CCCN(Cc2cc(-c3ccc(O)cc3F)nc3[nH]nc(C)c23)CC1C

Procedure:
To a solution of 75 mg 3-Fluoro-4-[3-methyl-4-(3-methyl-[1,4]diazepan-1-ylmethyl)-1H-pyrazolo[3,4-b]pyridin-6-yl]-phenol in 1.5 ml abs. THF were added 15 mg ethyl isocyanate and 26 mg Hünig's base. After 16 h at rt water was added, and the pH was adjusted to neutral. The mixture was extracted with ethyl acetate twice and the combined organic layers were dried and concentrated in vacuo. After purification by HPLC 29 mg (32%) of the title compound were obtained.
Reaction SMILES: [CH3:1][C:2](=[CH:5][C:6]#[C:7][C:8]([CH3:15])=[CH:9][CH2:10][O:11][C:12](=[O:14])[CH3:13])[CH:3]=[O:4].[CH2:16]([O:18]C(O)O)[CH3:17].P(=O)(O)(O)O.[C:27]1(C)C=CC(S(O)(=O)=O)=C[CH:28]=1>CCOCC.N1C=CC=CC=1.CO>[CH2:27]([O:4][CH:3]([O:18][CH2:16][CH3:17])[C:2]([CH3:1])=[CH:5][C:6]#[C:7][C:8]([CH3:15])=[CH:9][CH2:10][O:11][C:12](=[O:14])[CH3:13])[CH3:28]
Reactant: Cc1ccc(S(=O)(=O)O)cc1
Reactant: CC(=O)OCC=C(C)C#CC=C(C)C=O
Reactant: CCOC(O)O
Agent: O=P(O)(O)O
Solvent: CCOCC
Solvent: c1ccncc1
Solvent: CO
Product: CCOC(OCC)C(C)=CC#CC(C)=CCOC(C)=O
Reaction time: 20 h

Procedure:
36 g. of 2,6-dimethyl-8-acetoxy-2,6-octadien-4-in-1-al is reacted with 31 g. of orthoformic acid ethyl ester and a solution of 0.3 ml. of phosphoric acid and 150 mg. of p-toluenesulfonic acid in 20 ml. of absolute methanol. After standing for 20 hours at room temperature in a nitrogen atmosphere, 2 ml. of absolute pyridine is added and the reaction mixture taken up in ether. The ether extract is washed with sodium bicarbonate solution and water, dried over potassium carbonate, filtered and evaporated under reduced pressure (water pump vacuum). 48 g. of 1,1-diethoxy-2,6-dimethyl-8-acetoxy-2,6-octadien-4-in is obtained (Abs. Max. 269 mμ; E11 = 730).
Reaction SMILES: [CH3:1][C@@:2]([C:9]([OH:11])=[O:10])([CH2:4][CH2:5][C:6](O)=[O:7])[NH2:3].C(B(CC)CC)C.B>C1COCC1>[NH2:3][C:2]([CH3:1])([CH2:4][CH2:5][CH2:6][OH:7])[C:9]([OH:11])=[O:10]
Reactant: C[C@](N)(CCC(=O)O)C(=O)O
Agent: B
Agent: CCB(CC)CC
Solvent: C1CCOC1
Product: CC(N)(CCCO)C(=O)O
Temperature: 0 °C
Reaction time: 3 h
Yield: 124.6 %

Procedure:
Finely ground racemic a-methylglutamic acid (5.0 g, 0.029 tool) was suspended in THF (30 mL), treated with triethylborane (1M in THF, 32.32 mL, 0.032 mol), and heated at reflux for 36 h. After cooling to 0° C. the soln was treated dropwise with borane in THF (1M, 35.26 mL, 0.035 mol) and stirred at 0° C. for 3 h. The mixture was quenched with 5% aq HCl (30 mL), stirred for 0.5 h, concentrated on a rotary evaporator, and the residue dissolved in 5% HCl (44 mL) and heated at reflux for 0.75 h. After cooling and concentrating, the residue was taken up in MeOH (50 mL), concentrated, and this procedure repeated 3 × to give 5.69 g of the title compound which was not purified.
Reaction SMILES: Br[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[C:4]([F:10])[CH:3]=1.[CH3:11][O:12][C:13]1[CH:18]=[CH:17][C:16]([CH2:19][SH:20])=[CH:15][CH:14]=1.C1(C)C=CC=CC=1.CCN(C(C)C)C(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.O>[F:10][C:4]1[CH:3]=[C:2]([S:20][CH2:19][C:16]2[CH:17]=[CH:18][C:13]([O:12][CH3:11])=[CH:14][CH:15]=2)[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=1
Reactant: COc1cc(F)cc(Br)c1
Reactant: COc1ccc(CS)cc1
Agent: [Pd]
Agent: CC1(C)c2cccc(P(c3ccccc3)c3ccccc3)c2Oc2c(P(c3ccccc3)c3ccccc3)cccc21
Agent: O=C(/C=C/c1ccccc1)/C=C/c1ccccc1
Solvent: Cc1ccccc1
Solvent: O
Solvent: CCN(C(C)C)C(C)C
Product: COc1ccc(CSc2cc(F)cc(OC)c2)cc1
Temperature: 25 °C
Reaction time: 8 h
Yield: 91.4 %

Procedure:
To a mixture of 1-bromo-3-fluoro-5-methoxybenzene (5 g), (4-methoxyphenyl)methanethiol (3.76 g), and toluene (100 mL) were added Pd2(dba)3 (0.447 g), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.564 g) and DIPEA (8.52 mL). The mixture was stirred at room temperature overnight. The mixture was poured into water and extracted with EtOAc. The organic layer was separated, washed successively with water and brine, dried over MgSO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (6.20 g).
Reaction SMILES: [C:1]([O:5][C:6]([NH:8][C@H:9]([CH:13]([CH3:15])[CH3:14])[C:10]([OH:12])=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].CN(C(ON1N=N[C:26]2[CH:27]=[CH:28][CH:29]=[N:30][C:25]1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.C1(N)CCCC1.CCN(CC)CC>C(Cl)Cl>[CH:25]1([NH:30][C:10](=[O:12])[C@H:9]([NH:8][C:6](=[O:7])[O:5][C:1]([CH3:2])([CH3:3])[CH3:4])[CH:13]([CH3:15])[CH3:14])[CH2:26][CH2:27][CH2:28][CH2:29]1
Reactant: CN(C)C(On1nnc2cccnc21)=[N+](C)C
Reactant: CC(C)[C@@H](NC(=O)OC(C)(C)C)C(=O)O
Agent: F[P-](F)(F)(F)(F)F
Agent: NC1CCCC1
Solvent: ClCCl
Solvent: CCN(CC)CC
Product: CC(C)[C@@H](NC(=O)OC(C)(C)C)C(=O)NC1CCCC1
Temperature: 25 °C
Reaction time: 5 h
Yield: 93.2 %

Procedure:
To a mixture of (R)-2-(tert-butoxycarbonylamino)-3-methylbutanoic acid (0.5 g, 2.301 mmol), HATU (1.05 g, 2.76 mmol) and cyclopentanamine (0.455 mL, 4.60 mmol) in DCM (20 mL) was added Et3N (0.642 mL, 4.60 mmol). The reaction mixture was stirred at room temperature for 5 h, washed with saturated aqueous NaHCO3 and brine, dried over MgSO4, and concentrated. Purification by silica column chromatography (MeOH/DCM, 0-10%) afforded the title compound (0.61 g, 94%).
Reaction SMILES: C([O:3][C:4](=[O:36])[CH:5]([C:29]1[CH:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=1)[CH2:6][C:7]1[CH:11]=[C:10]([C:12]2[CH:17]=[CH:16][C:15]([NH:18][CH2:19][CH:20]=[CH2:21])=[CH:14][CH:13]=2)[N:9]([C:22]2[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=2)[N:8]=1)C.CS(O)(=O)=O>C(O)C.[Pd]>[N:18]1[C:15]2[C:16](=[CH:17][C:12]([C:10]3[N:9]([C:22]4[CH:27]=[CH:26][C:25]([CH3:28])=[CH:24][CH:23]=4)[N:8]=[C:7]([CH2:6][CH:5]([C:29]4[CH:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=4)[C:4]([OH:3])=[O:36])[CH:11]=3)=[CH:13][CH:14]=2)[CH:21]=[CH:20][CH:19]=1.[NH2:18][C:15]1[CH:16]=[CH:17][C:12]([C:10]2[N:9]([C:22]3[CH:23]=[CH:24][C:25]([CH3:28])=[CH:26][CH:27]=3)[N:8]=[C:7]([CH2:6][CH:5]([C:29]3[CH:30]=[C:31]([CH3:35])[CH:32]=[CH:33][CH:34]=3)[C:4]([OH:36])=[O:3])[CH:11]=2)=[CH:13][CH:14]=1
Reactant: C=CCNc1ccc(-c2cc(CC(C(=O)OCC)c3cccc(C)c3)nn2-c2ccc(C)cc2)cc1
Agent: [Pd]
Agent: CS(=O)(=O)O
Solvent: CCO
Product: Cc1ccc(-n2nc(CC(C(=O)O)c3cccc(C)c3)cc2-c2ccc(N)cc2)cc1
Product: Cc1ccc(-n2nc(CC(C(=O)O)c3cccc(C)c3)cc2-c2ccc3ncccc3c2)cc1
Temperature: 65 °C
Reaction time: 2 h
Yield: 35 %
Yield: 35 %

Procedure:
To a solution of 3-[5-(4-allylamino-phenyl)-1-p-tolyl-1H-pyrazol-3-yl]-2-m-tolyl-propionic acid ethyl ester (Example 94, Step A; 70 mg, 0.15 mmol) in ethanol (1 mL) was added 10% Pd/C (26 mg) and methanesulfonic acid (0.01 mL, 0.15 mmol, 1 equiv). The mixture was stirred at 65° C. for 2 h. The catalyst was removed by filtering the reaction mixture through a CELITE® pad, and the pad was rinsed with EtOH (1.5 mL). The combined filtrates were concentrated under reduced pressure. The crude residue was dissolved in 1:1 THF/H2O (1.5 mL), and LiOH was added (10 mg, 0.45 mmol, 3 equiv). After 3 h at 45° C., the mixture was purified by preparative reversed-phase HPLC (acetonitrile/water) to afford the title compound (26 mg, 35%) along with 3-[5-(4-amino-phenyl)-1-p-tolyl-1H-pyrazol-3-yl]-2-m-tolyl-propionic acid (20 mg, 35%). HPLC: Rt=3.18 (Method A). MS (ESI): mass calculated for C29H25N3O2, 447.19; m/z found, 448.2 [M+H]+. 1H NMR (400 MHz, CDCl3): 8.43 (d, J=8.5 Hz, 1H), 8.25 (d, J=8.8 Hz, 1H), 7.85 (d, J=1.7 Hz, 1H), 7.68 (dd, J=8.3, 4.8 Hz, 1H), 7.59 (dd, J=8.8, 1.7 Hz, 1H), 7.26-7.23 (m, 2H), 7.12 (s, 4H), 6.42 (s, 1H), 4.17 (dd, J=9.8, 5.3 Hz, 1H), 3.58 (dd, J=14.9, 9.8 Hz, 1H), 3.17 (dd, J=14.9, 5.3 Hz, 1H), 2.36 (s, 3H).
Reaction SMILES: CS[C:3]1[N:8]=[C:7](/[CH:9]=[C:10]2/[C:11](=[O:16])[NH:12][C:13](=[O:15])[NH:14]/2)[CH:6]=[CH:5][N:4]=1.O[O:18][S:19]([O-:21])=O.[K+].[CH2:23]1COCC1>O>[CH3:23][S:19]([C:3]1[N:8]=[C:7](/[CH:9]=[C:10]2/[C:11](=[O:16])[NH:12][C:13](=[O:15])[NH:14]/2)[CH:6]=[CH:5][N:4]=1)(=[O:21])=[O:18]
Reactant: CSc1nccc(/C=C2\NC(=O)NC2=O)n1
Reactant: C1CCOC1
Reactant: O=S([O-])OO
Agent: [K+]
Solvent: O
Product: CS(=O)(=O)c1nccc(/C=C2\NC(=O)NC2=O)n1
Temperature: 25 °C
Reaction time: 48 h

Procedure:
A mixture of (Z)-5-((2-(methylthio)pyrimidin-4-yl)methylene)imidazolidine-2,4-dione (5) (3.5 g, 14.83 mmol) in THF (100 mL, 0.15 M) was treated with a solution of oxone (27.35 g, 44.5 mmol, 3.0 equiv.) in water (175 mL). The resulting mixture was stirred at room temperature for 48 h. The resulting precipitate was filtered and washed with water (20 mL) and diethyl ether (20 mL) to afford (Z)-5-((2-(methylsulfonyl)pyrimidin-4-yl)methylene)imidazolidine-2,4-dione (6) as a solid (2.48 g, 3.97 g theoretical, 62%). LC-MS m/z 269 (M+1). The same procedure can be used with the N-benzyl (6b) and N-methyl (6c) analogs in comparable yields.
Reaction SMILES: C1(NC2C=CC(NC3C=CC=CC=3)=CC=2)C=CC=CC=1.[CH3:21][C:22]([S:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)([CH3:26])[CH2:23][CH2:24][OH:25].[C:34](OCC)(=[O:37])[CH:35]=[CH2:36]>>[C:34]([O:25][CH2:24][CH2:23][C:22]([CH3:21])([S:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[CH3:26])(=[O:37])[CH:35]=[CH2:36]
Reactant: C=CC(=O)OCC
Reactant: CC(C)(CCO)Sc1ccccc1
Agent: c1ccc(Nc2ccc(Nc3ccccc3)cc2)cc1
Product: C=CC(=O)OCCC(C)(C)Sc1ccccc1
Temperature: 112.5 °C

Procedure:
Into a 3-neck round-bottomed flask was placed (in order): N,N′-diphenyl-1,4-phenylenediamine (0.53 g, 2.04×10−3 moles), 3-Methyl-3-(phenylthio)butan-1-ol (50.0 g, 0.255 moles) and ethyl acrylate (276 mL, 2.55 moles). The apparatus was then assembled for reactive distillation through a Claisen head and purge-filled with nitrogen gas. The reaction flask was heated to 110-115° C. and after ca. 5 mL of ethyl acrylate had distilled over, titanium(IV) isoproproxide (TPT, 2.26 mL, 7.65×10−3 moles) was added to the reaction mixture via syringe in one portion. The rate of distillation immediately increased significantly and the distillate vapour temperature decreased from 99° C. to 90° C. These distillation conditions were maintained for a period of 150 minutes before the apparatus was evacuated by means of a 10 mbar PTFE-diaphragm pump and the remaining ethyl acrylate was stripped from the reaction mixture. The apparatus was then pumped down using a two-stage oil pump and the crude product distilled over at a vapour temperature of 109.5-112° C. (0.18 Torr, appearance: golden liquid, yield: 50.8 g).
Reaction SMILES: [CH2:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[C:7]([Br:11])([CH3:10])([CH3:9])[CH3:8].[Br-].[Al+3].[Br-].[Br-]>O>[Br:11][C:7]12[CH2:10][CH:3]3[CH2:4][CH:5]([CH2:6][C:1]([CH2:6][CH2:1][CH2:2][CH3:3])([CH2:2]3)[CH2:8]1)[CH2:9]2
Reactant: C1CCCCC1
Reactant: CC(C)(C)Br
Agent: [Al+3]
Agent: [Br-]
Solvent: O
Product: CCCCC12CC3CC(CC(Br)(C3)C1)C2
Reaction time: 2 h

Procedure:
Into a 200 ml egg plant-shaped flask, 8.8 g (0.046 moles) of 1-(n-butyl)adamantane obtained above was weighed and placed. Under the stream of nitrogen gas, 100 ml of cyclohexane was added, and a solution was prepared. While the solution was kept at 0° C. in an ice bath, 8.8 g (0.063 moles) of t-butyl bromide and 0.4 g (0.0014 moles) of aluminum bromide were added, and the reaction was allowed to proceed for 2 hours. To the reaction fluid, 100 ml of ion-exchanged water was added, and the extraction with cyclohexane was conducted using a separation funnel. The solvent was removed using an evaporator, and 10.4 g of 1-bromo-3-(n-butyl)adamantane of the object compound was obtained as a colorless transparent liquid substance (the yield: 84%).
Reaction SMILES: [CH2:1]([O:8][CH2:9][CH:10]=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[K+].Cl[CH2:15]Cl.[O:17]1[CH2:21][CH2:20]CC1>O>[CH2:1]([O:8][CH2:9][CH:10]=[CH:15][C:21](=[O:17])[CH3:20])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: C1CCOC1
Reactant: ClCCl
Reactant: O=CCOCc1ccccc1
Agent: [K+]
Agent: [OH-]
Solvent: O
Product: CC(=O)C=CCOCc1ccccc1
Reaction time: 0.5 h

Procedure:
Benzyloxyacetaldehyde (0.90 9; 6.0 mmol) and dimethyl (2-oxomethyl)-phosphonate (1.0 g; 6.0 mmol) were dissolved in a mixture of tetrahydrofuran (25 ml) and water (20 ml). 1N Aqueous potassium hydroxide (6 ml) was added and the mixture was stirred for 30 min. Di-chloromethane (50 ml) was added and the organic phase was separated, dried (MgSO4) and evaporated in vacuo leaving 5-benzyloxypent-3-en-2-one.
Reaction SMILES: [C:1]1([B:7]([CH:9]([O:16][CH:17]([B:24]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)O)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:32]([NH:36][CH2:37][CH2:38]O)[CH2:33][CH2:34][CH3:35]>C(O)C>[C:1]1([B:7]([CH:9]([O:16][CH:17]([B:24]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:38][CH2:37][NH:36][CH2:32][CH2:33][CH2:34][CH3:35])[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH2:38][CH2:37][NH:36][CH2:32][CH2:33][CH2:34][CH3:35])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1
Reactant: CCCCNCCO
Reactant: OB(c1ccccc1)C(OC(B(O)c1ccccc1)c1ccccc1)c1ccccc1
Solvent: CCO
Product: CCCCNCCB(c1ccccc1)C(OC(B(CCNCCCC)c1ccccc1)c1ccccc1)c1ccccc1

Procedure:
The entitled compound (38 mg) was obtained by allowing 44 mg of bis(3,3′-(phenylhydroxyboryl)benzyl) ether and 24 mg of N-butylethanolamine to act in 1 mL of ethanol.
Reaction SMILES: [C:1]([NH:11][C@H:12]([C:17]([OH:19])=O)[CH2:13][CH:14]([CH3:16])[CH3:15])([O:3][CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:2].CN1CC[O:24][CH2:23][CH2:22]1.ClC(OCC(C)C)=O.[BrH:35]>C1COCC1>[Br:35][CH2:22][C:23]([C:17](=[O:19])[C@H:12]([CH2:13][CH:14]([CH3:15])[CH3:16])[NH:11][C:1]([O:3][CH2:4][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1)=[O:2])=[O:24]
Reactant: CC(C)C[C@H](NC(=O)OCc1ccccc1)C(=O)O
Reactant: Br
Reactant: CN1CCOCC1
Agent: CC(C)COC(=O)Cl
Solvent: C1CCOC1
Product: CC(C)C[C@H](NC(=O)OCc1ccccc1)C(=O)C(=O)CBr
Temperature: -40 °C
Reaction time: 0.25 h
Yield: 86.4 %

Procedure:
N-Cbz-L-leucine (2.10 g, 7.6 mmol) was dissolved in THF (10 mL), cooled to −40° C., and 4-methylmorpholine (0.77 g, 7.6 mmol, 0.83 mL) was added, followed by dropwise addition of isobutyl chloroformate (1.04 g, 7.6 mmol, 0.98 mL). After 15 min, the solution was filtered into the previously prepared 0° C. solution of ethereal diazomethane. The resulting solution was allowed to stand at 0° C. for 23 h. HBr (30% in acetic acid) (45.2 mmol, 9 mL) was added and the resulting solution was stirred at 0° C. for 5 min, then washed sequentially with 0.1 N HCl, saturated aqueous NaHCO3 and saturated brine, then dried (MgSO4), filtered and concentrated to give the title compound as a colorless oil (2.43 g, 94%).
Reaction SMILES: [Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[C:9]([Br:11])[CH:10]=1)[NH:7][C:6](=[O:12])[C:5]2=O.C([C:18]1[CH:19]=[C:20]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:21]2[O:25][C:24](=[O:26])[CH2:23][C:22]=2[CH:27]=1)(C)(C)C.C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH3:43][OH:44]>C(O)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[C:9]([Br:11])[CH:10]=1)[NH:7][C:6](=[O:12])[C:5]2=[C:23]1[C:22]2[CH:27]=[C:18]([O:44][CH3:43])[CH:19]=[C:20]([C:28]([CH3:31])([CH3:30])[CH3:29])[C:21]=2[O:25][C:24]1=[O:26]
Reactant: O=C1Nc2c(Br)cc(Br)cc2C1=O
Reactant: CC(C)(C)c1cc2c(c(C(C)(C)C)c1)OC(=O)C2
Reactant: CO
Agent: Cc1ccc(S(=O)(=O)O)cc1
Solvent: CC(=O)O
Product: COc1cc2c(c(C(C)(C)C)c1)OC(=O)C2=C1C(=O)Nc2c(Br)cc(Br)cc21
Temperature: 5 °C

Procedure:
7.6 g (0.025 mol) of 5,7-dibromoisatin, 6.15 g (0.025 mol) of 5,7-di-tert-butyl-3H-benzofuran-2-one and 0.5 g of p-toluenesulfonic acid are boiled in 25 ml of acetic acid under nitrogen for 21 hours. 40 ml of methanol are then added and the suspension obtained is cooled to 5° C. The solid then obtained is filtered off and the filter residue is washed with methanol and dried at 60° C. The yield is 10.7 g (80% of theory). Melting point: 303-314° C. C: calculated/found 49.73/49.46; H: calculated/found 3.38/3.45; N: calculated/found 2.76/2.73
Reaction SMILES: Cl.[CH2:2]([NH:4][CH2:5][CH3:6])[CH3:3].[C:7]([C:9]1[CH:35]=[CH:34][C:12]([C:13]([NH:15][C:16]2[CH:17]=[CH:18][C:19]([CH3:33])=[C:20]([NH:22][C:23](=[O:32])[C:24]3[CH:29]=[CH:28][C:27]([CH2:30]Cl)=[CH:26][CH:25]=3)[CH:21]=2)=[O:14])=[CH:11][CH:10]=1)#[N:8].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[C:7]([C:9]1[CH:35]=[CH:34][C:12]([C:13]([NH:15][C:16]2[CH:17]=[CH:18][C:19]([CH3:33])=[C:20]([NH:22][C:23](=[O:32])[C:24]3[CH:29]=[CH:28][C:27]([CH2:30][N:4]([CH2:5][CH3:6])[CH2:2][CH3:3])=[CH:26][CH:25]=3)[CH:21]=2)=[O:14])=[CH:11][CH:10]=1)#[N:8]
Reactant: CCNCC
Reactant: Cc1ccc(NC(=O)c2ccc(C#N)cc2)cc1NC(=O)c1ccc(CCl)cc1
Agent: Cl
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CC(C)=O
Product: CCN(CC)Cc1ccc(C(=O)Nc2cc(NC(=O)c3ccc(C#N)cc3)ccc2C)cc1
Temperature: 55 °C
Yield: 67.2 %

Procedure:
Diethylamine hydrochloride (0.024 g) was added to a stirred mixture of N-[5-(4-cyanobenzamido)-2-methylphenyl]-4-(chloromethyl)benzamide (0.06 g), potassium carbonate (0.082 g) and acetone (5 ml) and the reaction mixture was stirred and heated to 55° C. for 16 hours. Further portions of diethylamine hydrochloride and potassium carbonate (same quanities as before) were added and the mixture was heated to 55° C. for a further 4 days. The reaction mixture was evaporated and the residue was triturated with water. The solid was isolated and dried under vacuum at 55° C. to give the title compound as a solid (0.044 g); NMR Spectrum: (CDCl3) 1.06 (t, 6H), 2.28 (s, 3H), 2.53 (m, 4H), 3.63 (s, 2H), 7.2 (d, 1H), 7.5 (d, 2H), 7.74 (m, 4H), 7.81 (d, 2H), 7.97 (d, 2H), 8.15 (s, 1H), 8.27 (s, 1H); Mass Spectrum: M−H− 439.
Reaction SMILES: [CH2:1]=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10].ClCCl.[OH:14]O>O.[O-2].[O-2].[Mn+4]>[CH2:1]1[O:14][CH:2]1[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH3:10]
Reactant: C=CCCCCCCCC
Reactant: OO
Agent: [Mn+4]
Agent: [O-2]
Solvent: O
Solvent: ClCCl
Product: CCCCCCCCC1CO1
Temperature: 25 °C
Reaction time: 14 h
Yield: 94 %

Procedure:
In a 25 mL scintillation vial equipped with a magnetic stirrer, 1-decene (1.41 g, 10 mmol) was placed followed by addition of 4 mL dichloromethane. To this solution was added BTSP (2.8 g, 15 mmol). The vial was immersed into ice/water bath. After 5 minutes Re2O7 (24 mg, 0.05 mmol)5 was added followed by 10 μL of water. The reaction turned bright yellow and was allowed to warm up to room temperature and stirred for 14 h. Upon completion, water (3 drops) was added followed by manganese dioxide (ca. 5 mg) in order to decompose the remaining H2O2. The destruction of H2O2 was evident by the disappearance of yellow color. The mixture was then dried over Na2SO4. Concentration afforded 1-decene oxide (1.48 g, 94% yield) of a colorless oil.