Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: Cl[C:2]([F:27])([F:26])[C:3]1[N:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[C:6]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:5]([NH:18][CH:19]([CH3:21])[CH3:20])[C:4]=1[C:22]([O:24][CH3:25])=[O:23].C(N(CC)CC)C.C(O)C>[Pd]>[F:27][CH:2]([F:26])[C:3]1[N:8]=[C:7]([C:9]([F:12])([F:10])[F:11])[C:6]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[C:5]([NH:18][CH:19]([CH3:21])[CH3:20])[C:4]=1[C:22]([O:24][CH3:25])=[O:23]
Reactant: CCOC(=O)c1c(C(F)(F)F)nc(C(F)(F)Cl)c(C(=O)OC)c1NC(C)C
Agent: [Pd]
Solvent: CCO
Solvent: CCN(CC)CC
Product: CCOC(=O)c1c(C(F)(F)F)nc(C(F)F)c(C(=O)OC)c1NC(C)C
Yield: 89.8 %

Procedure:
This compound was prepared as described in Example 54: 2.7 g (0.006 mol) of product of Example 60, 0.65 g (0.006 mol) of triethylamine and 0.12 g of Pd/C (10%) in 30 mol of ethanol were reacted affording an oil residue which was kugelrohr distilled at 80 Pa, pot temperature 104° C., to give 2.07 g (89.8%) of product as a white solid; mp 53°-55° C.
Reaction SMILES: [N-:1]=[N+:2]=[N-:3].[Na+].C(O)(=O)C.[CH2:9]([O:16][C:17]1[CH:24]=[CH:23][C:20]([C:21]#[N:22])=[CH:19][CH:18]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>C(O)CCC>[CH2:9]([O:16][C:17]1[CH:18]=[CH:19][C:20]([C:21]2[NH:22][N:3]=[N:2][N:1]=2)=[CH:23][CH:24]=1)[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1
Reactant: N#Cc1ccc(OCc2ccccc2)cc1
Reactant: [N-]=[N+]=[N-]
Agent: [Na+]
Solvent: CC(=O)O
Solvent: CCCCO
Product: c1ccc(COc2ccc(-c3nnn[nH]3)cc2)cc1
Yield: 85 %

Procedure:
6.6×10-2 mol of sodium azide and 6.6×10-2 mol of acetic acid were added to a solution of 5×10-2 mol of 4-benzyloxy benzonitrile (VIII) in 20 ml butanol. The reaction medium was then reflux-heated for 4 hours. 1 g sodium azide, 2 g acetic acid and 10 ml butanol were added and the reaction medium was again reflux-heated for 2 days. After concentration by evaporation of the solvent, the residue was dissolved in 20 ml of 10% aqueous NaOH. After filtration, the aqueous phase was extracted with ether. The alkaline solution was acidified with 2N HCl to obtain the expected compound, which was isolated with an 85% yield (M.P.=228° C.).
Reaction SMILES: Cl.C([O:4][C:5]([CH:7](C(OCC)=O)[CH2:8][CH2:9][CH:10]1[C:22]2[NH:21][C:20]3[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:14]=2[CH2:13][CH2:12][N:11]1[CH2:23][CH3:24])=[O:6])C>C(O)(=O)C>[C:5]([CH2:7][CH2:8][CH2:9][CH:10]1[C:22]2[NH:21][C:20]3[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:14]=2[CH2:13][CH2:12][N:11]1[CH2:23][CH3:24])([OH:6])=[O:4]
Reactant: CCOC(=O)C(CCC1c2[nH]c3ccccc3c2CCN1CC)C(=O)OCC
Agent: Cl
Solvent: CC(=O)O
Product: CCN1CCc2c([nH]c3ccccc23)C1CCCC(=O)O
Temperature: 120 °C
Reaction time: 5 h

Procedure:
3.0 ml of acetic acid and 1.5 ml of conc. hydrochloric acid were added to 0.70 g of 1,2,3,4-tetrahydro-1-[3,3-bis(ethoxycarbonyl)propyl]-2-ethyl-β-carboline. The mixture was stirred at 120° C. for 5 hours. After the reaction was completed, the mixture was evaporated to remove solvent, whereby 1,2,3,4-tetrahydro-1-(3-carboxypropyl)-2-ethyl-β-carboline was obtained as a crude product. 30 ml of 10% methanolic hydrogen chloride were added to the crude product, and the mixture was refluxed for 2 hours. After the reaction was completed, the mixture was concentrated. The residue thus obtained was alkalified with an aqueous saturated sodium bicarbonate solution under cooling, and extracted with ethyl acetate. The extract was washed with water, dried and evaporated to remove solvent. The residue thus obtained was purified by silica gel chromatography (Solvent: chloroform-methanol (20:1)), whereby 470 mg of 1,2,3,4-tetrahydro-1-(3-methoxycarbonylpropyl)-2-ethyl-β-carboline were obtained. Yield: 84.0%
Reaction SMILES: [CH3:1][C:2]1([OH:12])[CH2:11][CH2:10][C:5]2(OCC[O:6]2)[CH2:4][CH2:3]1.Cl.C([O-])([O-])=O.[K+].[K+]>C1COCC1>[OH:12][C:2]1([CH3:1])[CH2:11][CH2:10][C:5](=[O:6])[CH2:4][CH2:3]1
Reactant: CC1(O)CCC2(CC1)OCCO2
Agent: Cl
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: C1CCOC1
Product: CC1(O)CCC(=O)CC1
Temperature: 25 °C
Reaction time: 8 h
Yield: 90.1 %

Procedure:
To a solution of 8-methyl-1,4-dioxaspiro[4.5]decan-8-ol (6.1 g, 35.5 mmol) in THF (200 mL) was added 2 N HCl (32 mL). The resulting mixture was stirred at RT overnight, and then was basified to pH 8.0 by saturated K2CO3 solution. The separated organic layer was concentrated in vacuo and the residue was purified by column chromatography on silica gel (EA:PE=3:20 to 2:3) to afford the title compound as yellow oil (4.1 g, yield: 86.7%).
Reaction SMILES: [CH3:1][NH:2][C@H:3]([C:11](O)=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].[Li].[OH-].[Na+]>C1COCC1>[CH3:1][NH:2][C@@H:3]([CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)[CH2:11][OH:12]
Reactant: CN[C@@H](Cc1ccccc1)C(=O)O
Agent: [Al+3]
Agent: [H-]
Agent: [Li+]
Solvent: C1CCOC1
Product: CN[C@H](CO)Cc1ccccc1
Temperature: -5 °C

Procedure:
To a solution of N-methyl-L-phenylalanine (Sigma, 10 g, 55.8 mmol) in dry THF (600 mL) was added 3.18 g (83.7 mmol) lithium aluminium hydride at −5° C. The reaction mixture was stirred over night and cooled to −5° C. Additional 2.12 g (55.8 mmol) lithium alanate were added. The reaction mixture was refluxed overnight and cooled then to −5° C. To this mixture was added 21.5 ml NaOH solution (2N) drop by drop. and stirred at room temperature for additional 30 min. The mixture was filtered and the filtercake was washed with diethyl ether (50 mL). The filtrate was dried over MgSO4 and solvent was removed under reduced pressure to obtain the product 1b as light yellow solid.
Reaction SMILES: C1C2C(=CC=C([C:11]3[C:12]4[C:17]([C:18](Br)=[C:19]5[C:24]=3[CH:23]=[CH:22][CH:21]=[CH:20]5)=[CH:16][CH:15]=[CH:14][CH:13]=4)C=2)C=CC=1C1C=CC2C(=CC=CC=2)C=1.C1(C2C=CC=CC=2)C(B(O)O)=CC=CC=1.COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(C(=CC(=CC=1)C)C)C>CC([O-])=O.CC([O-])=O.[Pd+2].O.C(O)(C)(C)C>[CH:13]1[C:12]2[C:17](=[CH:18][C:19]3[C:24]([CH:11]=2)=[CH:23][CH:22]=[CH:21][CH:20]=3)[CH:16]=[CH:15][CH:14]=1
Reactant: Brc1c2ccccc2c(-c2ccc3ccc(-c4ccc5ccccc5c4)cc3c2)c2ccccc12
Agent: [Pd+2]
Agent: CC(=O)[O-]
Agent: COc1cccc(OC)c1-c1ccccc1P(C1CCCCC1)C1CCCCC1
Solvent: O
Solvent: CC(C)(C)O
Product: c1ccc2cc3ccccc3cc2c1
Temperature: 25 °C
Yield: 71.5 %

Procedure:
Under the nitrogen atmosphere, [9-([2,2′-binaphthalen]-7-yl)-10-bromoanthracene (2.0 g) as the tenth intermediate compound, o-biphenylboronic acid (0.9 g), Pd(OAc)2 (0.03 g), SPhos (manufactured by Aldrich Company) (0.12 g), potassium phosphate (1.7 g), and a mixture solvent of pseudo cumene, t-butyl alcohol, and water (14 ml) (pseudo cumene/t-butyl alcohol/water=10/3/1 (volume ratio)) were added to a flask and refluxed for 8 hours. Once the heating is completed, the reaction solution was cooled to room temperature. The reaction was terminated by adding water. The target compound was extracted with toluene. The solvent was distilled off under reduced pressure, and the obtained solid was purified by silica gel column chromatography (solvent: toluene) and further by active carbon column chromatography (solvent: toluene) to give 9-([1,1′-biphenyl]-2-yl)-10-([2,2′-binaphthalen]-7-yl)]anthracene (0.5 g) as the target compound represented by Formula (1-117). The scheme is shown in the following “Reaction 19”.
Reaction SMILES: [CH2:1]([O:8][CH2:9][C@@H:10]([C:19](O)=[O:20])[NH:11][C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.ClC(OCC)=O>O1CCCC1>[CH2:1]([O:8][CH2:9][C@H:10]([NH:11][C:12](=[O:13])[O:14][C:15]([CH3:17])([CH3:16])[CH3:18])[CH2:19][OH:20])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
Reactant: CC(C)(C)OC(=O)N[C@@H](COCc1ccccc1)C(=O)O
Agent: CCOC(=O)Cl
Solvent: C1CCOC1
Solvent: CCN(CC)CC
Product: CC(C)(C)OC(=O)N[C@H](CO)COCc1ccccc1
Temperature: 25 °C
Reaction time: 0.5 h
Yield: 89.2 %

Procedure:
O-benzyl-N-(t-butoxycarbonyl)-L-serine (2 g) was dissolved in tetrahydrofuran (20 ml), triethylamine (1.22 ml) was added, and ethyl chloroformate (713 μl) was further added dropwise at 0° C. After stirring the reaction mixture at room temperature for 30 min, the reaction mixture was filtered, and one piece of ice was added to the filtrate. Sodium borohydride (515 mg) was further added, and the mixture was stirred at room temperature for 6 hrs. The reaction mixture was diluted with ethyl acetate and, after washing with water, the organic layer was dried over anhydrous sodium sulfate. The solvent was evaporated and the obtained crude product was purified by silica gel chromatography (ethyl acetate-hexane) to give t-butyl (1R)-2-(benzyloxy)-1-(hydroxymethyl)ethylcarbamate (1.7 g)
Reaction SMILES: O.P([O-])([O-])([O-])=O.[CH2:7]([O:9][C:10]([CH:12]1[CH2:17][CH2:16][C:15]2[CH:18]=[CH:19][C:20]([OH:22])=[CH:21][C:14]=2[O:13]1)=[O:11])[CH3:8].[OH-].[Na+]>O1CCCC1>[OH:22][C:20]1[CH:19]=[CH:18][C:15]2[CH2:16][CH2:17][C@H:12]([C:10]([O:9][CH2:7][CH3:8])=[O:11])[O:13][C:14]=2[CH:21]=1
Reactant: CCOC(=O)C1CCc2ccc(O)cc2O1
Agent: O=P([O-])([O-])[O-]
Agent: [Na+]
Agent: [OH-]
Solvent: O
Solvent: C1CCOC1
Product: CCOC(=O)[C@H]1CCc2ccc(O)cc2O1
Yield: 35.1 %

Procedure:
A 5 L three-necked flask equipped with a mechanical stirrer, a pH electrode connected to a pH control unit and an addition tube connected to a peristaltic pump, was charged with 2.73 L of deionized water, 682 mL of 0.05M phosphate buffer (pH 7.0) and a solution of 100.0 g (0.45 mol) of racemic-3,4-dihydro-7-hydroxy-2H-1-benzopyran-2-carboxylic acid ethyl ester in 340 mL of tetrahydrofuran. The pH was adjusted to 8 with adequate 1.0N aqueous sodium hydroxide solution, and 9.0 g of Pseudomonas lipase enzyme (P-30, Amano International) was added to the mixture. The hydrolysis was allowed to proceed while stirring at a fast rate and keeping the pH at 8 by adding adequate 1.0N aqueous sodium hydroxide solution via the pump. The hydrolysis was stopped when 40% of the base has been consumed. The tetrahydrofuran in the reaction mixture was removed at 40° C. (10 mm Hg of vacuum) and the aqueous phase was extracted 3×1.0 L=3.0 L of ethyl acetate. The combined organic extracts were washed successively with 500 mL of saturated aqueous sodium bicarbonate solution and 500 mL of brine, then dried over anhydrous sodium sulfate. The drying agent was removed by filtration and the solvent was removed at 35° C. (10 mm Hg) to give 35.1 g (35% yield; 86% of theory) of (R)-3,4-dihydro-7-hydroxy-2H-1-benzopyran-2-carboxylic acid, ethyl ester as a beige solid, m.p. 77°-78° C.; (α)D22 -18.8° (c 1.0, CHCl3); 93.5% e.e.
Reaction SMILES: [CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[Li]C.[Zn](C)C.CCCCCCC.CCOCC.[CH:26]([CH:29]1[CH2:34][CH2:33][C:32](=[O:35])[CH:31]=[CH:30]1)([CH3:28])[CH3:27]>[H-].[Cl-].[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Zr+2].[Cu]I.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Zr+2].[Cu]>[CH:1]([CH:30]1[CH:29]([CH:26]([CH3:28])[CH3:27])[CH2:34][CH2:33][C:32](=[O:35])[CH2:31]1)=[CH:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8]
Reactant: CC(C)C1C=CC(=O)CC1
Reactant: C#CCCCCCC
Agent: [Cu]
Agent: [Cu]I
Agent: [Zr+2]
Solvent: CCCCCCC
Solvent: CCOCC
Product: CCCCCCC=CC1CC(=O)CCC1C(C)C
Temperature: -78 °C
Yield: 92.1 %

Procedure:
A 10 mL round-bottom flask equipped with a stir bar was charged with zirconocene chloride hydride (0.301 g, 1.04 mmol) and sealed with a septum. The flask was evacuated with a vacuum pump and purged with argon, the process being repeated 3 times. THF (4 mL) was injected and the mixture stirred to generate a white slurry which was treated via syringe with 1-octyne (0.115 g, 1.04 mmol). The mixture was stirred for 15 minutes to yield a yellow-to-green solution which was cooled to -78° C. and treated via syringe with ethereal MeLi (0.65 mL, 1.03 mmol) to generate a dark red solution. At the same time, a 5 mL flask with septum was purged as above with Ar and then 1 mL of THF was added via syringe. To this flask at -78° C. was added ZnMe2 in heptane (0.44 mL, 0.53 mmol), followed by MeLi in Et2O (0.33 mL, 0.53 mmol). After 5 minutes the solution was warmed to 0° C. for 10 minutes to afford a clear solution, which was then cooled to -78° C. Concurrently, CuI (20.7 mg, 0.109 mmol) was placed in a 10 mL round-bottom flask equipped with a stir bar, and sealed under septum. The flask was evacuated and purged with argon as above and THF (1 mL) added via syringe. To this slurry at -78° C. was then added MeLi in Et2O (0.136 mL, 0.217 mmol). The slurry was warmed slightly to generate a clear solution of Me2CuLi, then cooled to -78° C. At -78° C. and by cannula the solution of Me3ZnLi was added to the Me2CuLi solution. The solution of the zirconocene was added via cannula to the resulting Me2CuLi/Me3ZnLi solution, thereby providing a reaction mixture comprising 20 mol-% of copper per mole of substrate enone. The mixture was stirred for 15 minutes at -78° C. to yield a dark red solution which was treated with 4-isopropyl-2-cyclohexenone (77 μL, 0.5 mmol) as a neat liquid over 70 minutes. After 1 hour of additional stirring the mixture was quenched with 5 mL of 10% NH4OH in saturated NH4Cl. The product was extracted with 3×20 mL of ether and dried over Na2SO4. The solution was then filtered through fritted filter paper and the solvent removed in vacuo. The resulting residue was submitted to flash chromatography on silica gel (Petroleum Ether/Ethyl Acetate 40/1) to give a 92% yield (115.3 mg) of the product as a colorless oil giving satisfactory IR, NMR, MS and HRMS data.
Reaction SMILES: C([O-])(=O)C.[Na+].[Br:6][C:7]1[CH:12]=[CH:11][C:10]([F:13])=[CH:9][C:8]=1[O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1I.[C:23]([O:27][CH2:28][CH3:29])(=[O:26])[CH:24]=[CH2:25].O>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN1C(=O)CCC1>[CH2:28]([O:27][C:23](=[O:26])[CH:24]=[CH:25][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=1[CH2:15][O:14][C:8]1[CH:9]=[C:10]([F:13])[CH:11]=[CH:12][C:7]=1[Br:6])[CH3:29]
Reactant: C=CC(=O)OCC
Reactant: Fc1ccc(Br)c(OCc2ccccc2I)c1
Agent: CC(=O)[O-]
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: [Br-]
Solvent: O
Solvent: CN1CCCC1=O
Product: CCOC(=O)C=Cc1ccccc1COc1cc(F)ccc1Br
Temperature: 60 °C
Yield: 100.2 %

Procedure:
To a clean, dry 100-gallon reactor with stirring under nitrogen add fresh N-methylpyrrolidinone (72 L), sodium acetate (2721 g, 33.17 mol), 1-bromo-4-fluoro-2-(2-iodo-benzyloxy)-benzene (9000 g, 22.11 mol) and tetrabutylammonium bromide (7128 g, 22.11 mol). Initiate stirring and de-gas the reaction mixture under full vacuum for 30 min, purging with nitrogen. Allow the reactor to return to ambient pressure under nitrogen and repeat the degassing procedure. Add palladium (II) acetate (180 g, 2%/weight) to the reaction mixture and heat to 60° C. At 60° C., slowly add ethyl acrylate (2258 g, 22.55 mol) as a solution in N-methyl pyrrolidinone (18 L) to the reaction mixture via the addition funnel. Upon completion of the addition, heat the reaction mixture to 70° C. Continue to stir for a minimum of 2 h at 70° C. Adjust the internal temperature of the reaction mixture to 5-10° C. To a separate, clean, appropriately sized reactor, charge water (225 L), initiate vigorous stirring and cool to an internal temperature of ≦5° C. Transfer the reaction mixture to the vigorously stirring water over a minimum of one hour. Stir the resulting suspension for 30 min to one hour at ambient temperature. Filter through a polypropylene filter pad to collect the light purple solids. Wash the filter cake with water (25 L) and pull dry on the filter using a rubber dam. Recharge the solids to the reactor with water (45 L) and stir the suspension for 30 min to one hour. Re-filter the solids onto a polypropylene filter pad, washing the filter cake with water (25 L). Pull dry on the filter using a rubber dam. Transfer the light purple material to drying trays and air dry in a fume hood for a minimum of 24 h. Oven dry the solids under vacuum at <50° C. to obtain the title compound (8.4 kg, 100%).
Reaction SMILES: [CH3:1][O:2][C:3](=[O:31])[C@H:4]([CH2:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][C:22]2[C:27]([Cl:28])=[CH:26][CH:25]=[CH:24][C:23]=2[Cl:29])=[C:16]([OH:30])[CH:15]=1)[NH:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7].[C:32]([O-])([O-])=O.[K+].[K+].CI>[N+](CCCC)(CCCC)(CCCC)CCCC.[I-].CN(C=O)C>[CH3:1][O:2][C:3](=[O:31])[C@H:4]([CH2:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][C:22]2[C:23]([Cl:29])=[CH:24][CH:25]=[CH:26][C:27]=2[Cl:28])=[C:16]([O:30][CH3:32])[CH:15]=1)[NH:5][C:6]([O:8][C:9]([CH3:12])([CH3:10])[CH3:11])=[O:7]
Reactant: O=C([O-])[O-]
Reactant: COC(=O)[C@H](Cc1ccc(OCc2c(Cl)cccc2Cl)c(O)c1)NC(=O)OC(C)(C)C
Agent: CCCC[N+](CCCC)(CCCC)CCCC
Agent: [I-]
Agent: [K+]
Solvent: CI
Solvent: CN(C)C=O
Product: COC(=O)[C@H](Cc1ccc(OCc2c(Cl)cccc2Cl)c(OC)c1)NC(=O)OC(C)(C)C
Temperature: 25 °C
Reaction time: 8 h
Yield: 85.5 %

Procedure:
To a suspension of N-(tert-butoxycarbonyl)-4-(2,6-dichlorobenzyloxy)-3-hydroxy-L-phenylalanine methyl ester (0.45 g), K2CO3 (0.199 g), and n-Bu4NI (0.035 g) in DMF (4.0 mL) was added CH3I (0.072 mL) and the mixture was stirred overnight at room temperature. DMF was removed and the residue was partitioned between water and EtOAc. The organic layer was separated and the aqueous solution was extracted with EtOAc. The combined extract was dried (MgSO4) and evaporated. The residue was purified by preparative TLC (silica gel; eluent: hexanes/CH2Cl2/EtOAc, 3:3:1) to yield 0.396 g of N-(tert-butoxycarbonyl)-4-(2,6-dichlorobenzyloxy)-3-methoxy-L-phenylalanine methyl ester. ESMS: m/z 484 (MH+).
Reaction SMILES: [Cl:1][C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[C:7]([Cl:12])[C:6]=2C=O.C(=O)([O-])[O-].[Na+].[Na+].[Cl-].[OH:22][NH3+:23].O>C(O)C>[Cl:1][C:2]1[CH:3]=[N:4][C:5]2[C:6](=[N:23][OH:22])[CH:7]([Cl:12])[CH:8]=[CH:9][C:10]=2[CH:11]=1
Reactant: O=Cc1c(Cl)ccc2cc(Cl)cnc12
Reactant: [NH3+]O
Agent: O=C([O-])[O-]
Agent: [Cl-]
Agent: [Na+]
Solvent: O
Solvent: CCO
Product: ON=C1c2ncc(Cl)cc2C=CC1Cl
Yield: 101.1 %

Procedure:
22.6 g of 3,7-dichloroquinoline-8-carbaldehyde were dissolved in 300 parts of ethanol, 10.6 g of sodium carbonate and 6.9 g of hydroxylammonium chloride were added to this solution, and the suspension was refluxed for 1 hour. Thereafter, 1,000 g of water were added, and the precipitated solid was filtered off and dried to give 23 g (96% of theory) of 3,7-dichloro-8-hydroxyliminoquinoline of melting point 202° C.
Reaction SMILES: [C:1]([O-:4])(=[O:3])[CH3:2].[K+].Cl[CH2:7][SiH2:8][CH:9]([O:12][CH3:13])[O:10][CH3:11]>[Br-].C([P+](CCCC)(CCCC)CCCC)CCC.C(OCCOCCOCCCC)CCC>[C:1]([O:4][CH2:7][SiH2:8][CH:9]([O:12][CH3:13])[O:10][CH3:11])(=[O:3])[CH3:2]
Reactant: COC(OC)[SiH2]CCl
Reactant: CC(=O)[O-]
Agent: CCCCOCCOCCOCCCC
Agent: CCCC[P+](CCCC)(CCCC)CCCC
Agent: [Br-]
Product: COC(OC)[SiH2]COC(C)=O
Yield: 90.8 %

Procedure:
Example 2 was repeated using potassium acetate (405 g, 4.13 mol) and (chloromethyl)dimethoxymethylsilane (535 g, 3.46 mol) as starting materials, tetrabutylphosphonium bromide (35.0 g, 10.3 mmol) as catalyst and diethylene glycol dibutyl ether (525 mL) as solvent. After the reaction, the product was distilled at 10 mbar (head), 61-70° C. (head) and 80-119° C. (pot) through a packed column (20 cm) to obtain 560 g (3.14 mol, 91% of theory) of (acetoxymethyl)-dimethoxymethylsilane in the distillate; purity 98.0% (GC area %). The solvent then started to pass over at 10 mbar (head), 118° C. (head) and 124° C. (pot); by distilling over about 10 g of solvent, the (acetoxymethyl)dimethoxymethylsilane was fully removed from the residue. The solvent, potassium chloride, excess potassium acetate and the phase transfer catalyst (in the form of the bromide, chloride and acetate salt of tetrabutylphosphonium) remained in the residue.
Reaction SMILES: [H+].[H+].Cl[Pt-2:4](Cl)(Cl)(Cl)(Cl)Cl.C(=O)=O.[CH2:13]=[CH:14][C:15](=[CH2:22])[CH2:16][CH2:17][CH:18]=[C:19]([CH3:21])[CH3:20]>C(O)(C)C.C([O-])(O)=O.[Na+]>[Pt:4].[CH2:13]=[CH:14][C:15](=[CH2:22])[CH2:16][CH2:17][CH:18]=[C:19]([CH3:21])[CH3:20]
Reactant: Cl[Pt-2](Cl)(Cl)(Cl)(Cl)Cl
Agent: C=CC(=C)CCC=C(C)C
Agent: O=C([O-])O
Agent: O=C=O
Solvent: CC(C)O
Product: [Pt]

Procedure:
The chloroplatinic acid was first dissolved in the isopropanol, NaHCO3 was then added in small portions to avoid the formation of foam, since carbon dioxide was evolved, and the β-myrcene was then added.
Reaction SMILES: [CH2:1]([O:8][C@H:9]1[C@H:16]([OH:17])[CH2:15][CH2:14][N:13]([C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[O:19])[C@@H:10]1[CH:11]=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[BH4-].[Na+].O.[Cl-].[NH4+]>C(O)C>[CH2:1]([O:8][C@@H:9]1[C@@H:10]([CH2:11][OH:12])[N:13]([C:18]([O:20][CH2:21][C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)=[O:19])[CH2:14][CH2:15][C@H:16]1[OH:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: O=C[C@@H]1[C@@H](OCc2ccccc2)[C@H](O)CCN1C(=O)OCc1ccccc1
Agent: [BH4-]
Agent: [Cl-]
Agent: [NH4+]
Solvent: O
Solvent: CCO
Product: O=C(OCc1ccccc1)N1CC[C@@H](O)[C@H](OCc2ccccc2)[C@H]1CO
Yield: 96.9 %

Procedure:
3-O-Benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexose (24) (364 mg, 0.986 mmol) was dissolved in ethanol (5 ml) and treated with a solution of sodium borohydride (30.0 mg, 0.784 mmol) in a 1:1 mixture of EtOH and H2O (2 ml). After 20 minutes excess ammonium chloride was added, the solution concentrated, poured into brine (15 ml) and extracted with dichloromethane (4×20 ml). The organic layers were combined, dried, filtered and evaporated to give 4-O-benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol (355 mg, 97%) as a clear oil, [α]20D -36.7° (c, 0.22 in chloroform); νmax (film) 3380 (OH), 2910, 1665 (2×CO), 1430, 1210 and 1075 cm-1 ; 1H NMR δ 1.55-1.68 (1H, m, H-2); 2.04-2.17 (1H, m, H-2'); 2.85 (2H, bs, 2×OH); 3.40-3.57 (2H, m, H-5, H-1); 3.83-4.03 (4H, m, 6,6'-H, H-4, H-1'); 4.34 (1H, bs, H-3); 4.55, 4.72 (2H, 2×d, CH2Ph, JH,H 12.0 Hz); 5.15 (2H, s, CH2 -Z); 7.28-7.38 (10, m, 2×H-Ph). m/z: 264 (M-benzyloxy+, 100%), 91 (10%), 372 (M+H+, 5%).
Reaction SMILES: Cl[C:2]1[CH:11]=[C:10]([Cl:12])[C:9]2[C:4](=[CH:5][C:6]([S:13][C:14]3[CH:15]=[C:16]([C:20]4([C:26]#[N:27])[CH2:25][CH2:24][O:23][CH2:22][CH2:21]4)[CH:17]=[CH:18][CH:19]=3)=[CH:7][CH:8]=2)[N:3]=1.[C:28](=[NH:41])([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.CC(C)([O-])C.[Na+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:28](=[N:41][C:2]1[CH:11]=[C:10]([Cl:12])[C:9]2[C:4](=[CH:5][C:6]([S:13][C:14]3[CH:15]=[C:16]([C:20]4([C:26]#[N:27])[CH2:21][CH2:22][O:23][CH2:24][CH2:25]4)[CH:17]=[CH:18][CH:19]=3)=[CH:7][CH:8]=2)[N:3]=1)([C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1
Reactant: N#CC1(c2cccc(Sc3ccc4c(Cl)cc(Cl)nc4c3)c2)CCOCC1
Reactant: N=C(c1ccccc1)c1ccccc1
Agent: [Pd]
Agent: CC(C)(C)[O-]
Agent: O=C(/C=C/c1ccccc1)/C=C/c1ccccc1
Solvent: Cc1ccccc1
Product: N#CC1(c2cccc(Sc3ccc4c(Cl)cc(N=C(c5ccccc5)c5ccccc5)nc4c3)c2)CCOCC1
Temperature: 80 °C

Procedure:
3b (1.0 g, 2.4 mmol), benzophenone imine (0.4 mL, 2.4 mmol), sodium tert-butoxide (350 mg, 3.6 mmol), BINAP (150 mg, 0.27 mmol), and Pd2dba3 (55 mg, 0.06 mmol) were dissolved in toluene (10 mL) and degassed for 10 minutes with N2. The reaction was then sealed and heated to 80° C. for 2 hours. After cooling to room temperature, the reaction was diluted with EtOAc and brine, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, and concentrated, and the residue was purified by silica gel chromatography (30% EtOAc in hexanes) to give the desired product, 3c.
Reaction SMILES: [N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH3:10])([O-])=O>CS(C)=O>[CH3:10][C:5]1[C:4]([NH:1][NH:1][C:4]2[C:5]([CH3:10])=[CH:6][CH:7]=[CH:8][CH:9]=2)=[CH:9][CH:8]=[CH:7][CH:6]=1
Reactant: Cc1ccccc1[N+](=O)[O-]
Solvent: CS(C)=O
Product: Cc1ccccc1NNc1ccccc1C
Yield: 93 %

Procedure:
An identical reduction of o-nitrotoluene as described in example 7 was carried out, except 1.8 g of dimethyl sulfoxide was added to the reaction mixture. This reduction resulted in a 93% yield of o-hydrazotoluene.