Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: [NH2:1][CH:2]([CH2:5][O:6][C:7]1[CH:12]=[CH:11][C:10]([O:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:9][CH:8]=1)[CH2:3][OH:4].C(N(CC)CC)C.[F:27][C:28]1[CH:36]=[CH:35][CH:34]=[C:33]([F:37])[C:29]=1[C:30](Cl)=O>O1CCCC1>[F:27][C:28]1[CH:36]=[CH:35][CH:34]=[C:33]([F:37])[C:29]=1[C:30]1[O:4][CH2:3][CH:2]([CH2:5][O:6][C:7]2[CH:12]=[CH:11][C:10]([O:13][C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)=[CH:9][CH:8]=2)[N:1]=1
Reactant: NC(CO)COc1ccc(Oc2ccccc2)cc1
Reactant: O=C(Cl)c1c(F)cccc1F
Solvent: CCN(CC)CC
Solvent: C1CCOC1
Product: Fc1cccc(F)c1C1=NC(COc2ccc(Oc3ccccc3)cc2)CO1
Temperature: 25 °C
Reaction time: 0.08 h
Yield: 76.3 %

Procedure:
To a mixture of 1.14 g (4.40 mmol.) of 2-amino-3-(4-phenoxyphenoxy)propanol, 0.58 g (5.72 mmol.) of triethylamine and 20 ml of anhydrous tetrahydrofuran, there was added dropwise a solution of 0.78 g (4.40 mmol.) of 2,6-difluorobenzoylchloride in 10 ml of anhydrous tetrahydrofuran with stirring at a temperature of from 5° C. to 10° C. for 5 minutes. After addition, the reaction mixture was stirred at room temperature for 2 hours. The above mixture was filtrated with a filter glass to remove the resultant precipitate and the filtrate was concentrated under reduced pressure. To the residue, there was added 20 ml of toluene and 10 ml of thionyl chloride and the reaction mixture was refluxed by heating with stirring for 5 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. To the residue, there was added 20 ml of methanol and further added dropwise 1 ml of a 5N aqueous solution of sodium hydroxide with stirring at a temperature of 60° C. for 5 minutes. Then the reaction mixture was stirred at the same temperature for 5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. To the residue, there was added 100 ml of ethyl acetate. The mixture was washed with water, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel chromatography to give 1.28 g of 2-(2,6-difluorophenyl)-4-[(4-phenoxyphenoxy)methyl]-2-oxazoline as a colorless oily substance (nD19.1 1.5814).
Reaction SMILES: [Cl:1][C:2]1[CH:31]=[CH:30][C:5]([CH2:6][N:7]2[C:15]3[C:10](=[CH:11][C:12]([CH:16]=[C:17]4[S:21][C:20]([N:22]5[CH2:28][CH2:27][CH2:26][NH:25][CH2:24][CH2:23]5)=[N:19][C:18]4=[O:29])=[CH:13][CH:14]=3)[CH:9]=[N:8]2)=[C:4]([C:32]([F:35])([F:34])[F:33])[CH:3]=1.[CH3:36][S:37](Cl)(=[O:39])=[O:38]>>[Cl:1][C:2]1[CH:31]=[CH:30][C:5]([CH2:6][N:7]2[C:15]3[C:10](=[CH:11][C:12]([CH:16]=[C:17]4[S:21][C:20]([N:22]5[CH2:28][CH2:27][CH2:26][N:25]([S:37]([CH3:36])(=[O:39])=[O:38])[CH2:24][CH2:23]5)=[N:19][C:18]4=[O:29])=[CH:13][CH:14]=3)[CH:9]=[N:8]2)=[C:4]([C:32]([F:35])([F:34])[F:33])[CH:3]=1
Reactant: O=C1N=C(N2CCCNCC2)SC1=Cc1ccc2c(cnn2Cc2ccc(Cl)cc2C(F)(F)F)c1
Reactant: CS(=O)(=O)Cl
Product: CS(=O)(=O)N1CCCN(C2=NC(=O)C(=Cc3ccc4c(cnn4Cc4ccc(Cl)cc4C(F)(F)F)c3)S2)CC1

Procedure:
5-[1-(4-Chloro-2-trifluoromethyl-benzyl)-1H-indazol-5-ylmethylene]-2-(4-methanesulfonyl-[1,4]diazepan-1-yl)-thiazol-4-one was prepared from 5-[1-(4-Chloro-2-trifluoromethyl-benzyl)-1H-indazol-5-ylmethylene]-2-[1,4]diazepan-1-yl-thiazol-4-one and methane sulfonyl chloride according to Example 133.
Reaction SMILES: Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.C([Li])CCC.[CH3:14][Sn:15](Cl)([CH3:17])[CH3:16].O>CCOCC>[CH3:14][Sn:15]([CH3:17])([CH3:16])[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1
Reactant: Cc1ccc(Br)cc1
Reactant: C[Sn](C)(C)Cl
Agent: [Li]CCCC
Solvent: O
Solvent: CCOCC
Product: Cc1ccc([Sn](C)(C)C)cc1
Temperature: -78 °C
Reaction time: 0.25 h
Yield: 77 %

Procedure:
100 g (0.585 mol) of 1-bromo-4-methylbenzene was dissolved in 500 mL of anhydrous ether in an argon atmosphere, and then cooled to −78° C. 252 mL (2.5M in hexane, 0.615 mol) of an n-butyl lithium solution was slowly added dropwise. The mixture was stirred for 15 minutes, and a solution of 122.6 g (0.615 mol) of trimethyltin chloride in 500 mL of ether was added. The mixture was stirred for 2 hours while the temperature was gradually increased to room temperature, followed by the addition of 700 mL of distilled water and then stirring. The organic layer was separated, treated with magnesium sulfate, filtered, and concentrated under reduced pressure, yielding trimethyl(p-tolyl)tin as represented below in a 77% yield.
Reaction SMILES: [CH3:1][C:2]1[S:10][C:9]2[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=2)[CH:3]=1.[O-:11][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:14])=[O:13].[C:19]1([I+]C2C=CC=CC=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(OCC)C>O.C([O-])(=O)C1C=CC=CC=1.[Cu+2].C([O-])(=O)C1C=CC=CC=1>[O-:14][S:12]([C:15]([F:18])([F:17])[F:16])(=[O:13])=[O:11].[C:19]1([S+:10]2[C:9]3[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=3[CH:3]=[C:2]2[CH3:1])[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1
Reactant: Cc1cc2ccccc2s1
Reactant: c1ccc([I+]c2ccccc2)cc1
Agent: [Cu+2]
Agent: O=C([O-])c1ccccc1
Agent: O=S(=O)([O-])C(F)(F)F
Solvent: CCOCC
Solvent: O
Product: Cc1cc2ccccc2[s+]1-c1ccccc1
Reaction time: 1 h
Yield: 73.3 %

Procedure:
2-Methylthianaphthene (5 g, 0.0327 mole), diphenyliodonium triflate (18.28 g, 0.0425 mole) and copper benzoate (0.1 g, 0.000327 mole) were heated without solvent for 0.5 hours at 140° C. under a nitrogen atmosphere. After cooling down, 150 ethyl ether was added to solidify the product. Filtration and washing with ethyl ether yielded a brownish-grey solid, which was dissolved in 500 ml hot water, and the solution filtered and the water removed in vacuo. The resulting off-white solid was stirred in 50 ml ethyl ether for 1 hour, the mixture filtered and the residue washed with ethyl ether. The product was recrystallized from dichloromethane/t-butyl methyl ether to yield 8.97 g (76%) of 1-phenyl-2-methylbenzothiophenium triflate. The structure was confirmed by 1H/13C NMR spectroscopy.
Reaction SMILES: [C:1]([C:5]1[CH:13]=[CH:12][C:8]([C:9](Cl)=[O:10])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[OH:14][CH2:15][C:16]1[CH:27]=[CH:26][C:19]([C:20]([O:22][CH2:23][CH:24]=[CH2:25])=[O:21])=[CH:18][CH:17]=1>>[C:1]([C:5]1[CH:13]=[CH:12][C:8]([C:9]([O:14][CH2:15][C:16]2[CH:17]=[CH:18][C:19]([C:20]([O:22][CH2:23][CH:24]=[CH2:25])=[O:21])=[CH:26][CH:27]=2)=[O:10])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2]
Reactant: CC(C)(C)c1ccc(C(=O)Cl)cc1
Reactant: C=CCOC(=O)c1ccc(CO)cc1
Product: C=CCOC(=O)c1ccc(COC(=O)c2ccc(C(C)(C)C)cc2)cc1

Procedure:
In a manner similar to Example 1(d), by reaction of 2 g (15 mmol) of 4 -tert-butylbenzoyl chloride with 2.9 g (15 mmol) of allyl 4-hydroxymethylbenzoate, 4 g (77% ) of allyl ester are obtained in the form of a colorless oil.
Reaction SMILES: Cl.[CH3:2][CH:3]1[CH2:8][CH2:7][NH:6][CH:5]([C:9]([OH:11])=[O:10])[CH2:4]1.[CH2:12](O)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.O.[C:21]1([CH3:31])[CH:26]=[CH:25][C:24]([S:27]([OH:30])(=[O:29])=[O:28])=[CH:23][CH:22]=1.O>C1C=CC=CC=1>[C:21]1([CH3:31])[CH:22]=[CH:23][C:24]([S:27]([OH:30])(=[O:28])=[O:29])=[CH:25][CH:26]=1.[CH3:2][CH:3]1[CH2:8][CH2:7][NH:6][CH:5]([C:9]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:10])[CH2:4]1
Reactant: CC1CCNC(C(=O)O)C1
Reactant: OCc1ccccc1
Agent: Cc1ccc(S(=O)(=O)O)cc1
Agent: Cl
Solvent: O
Solvent: c1ccccc1
Product: CC1CCNC(C(=O)OCc2ccccc2)C1
Yield: 22 %

Procedure:
A solution of 20 g (0.112 mole) of 4-methyl-2-piperidinecarboxylic acid hydrochloride, 24 g (0.224 mole) of benzyl alcohol and 25.6 g (0.134 mole) of p-toluenesulfonic acid monohydrate in 100 ml of benzene was refluxed for 5 hours with the continuous removal of water through a Dean-Stark water trap. At the end of this period, the solvent was distilled off, and the residue was washed with ether-n-hexane and recrystallized to give 10 g (22%) of benzyl 4-methyl-2-piperidinecarboxylate p-toluenesulfonate, M.P. 160°-163° C.
Reaction SMILES: II.Br[C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH3:12])=[CH:6][CH:5]=1.[Mg].[CH:14]1([C:17]2[CH:18]=[CH:19][C:20]([CH:25]=[O:26])=[N:21][C:22]=2[O:23][CH3:24])[CH2:16][CH2:15]1>C1COCC1>[CH:14]1([C:17]2[CH:18]=[CH:19][C:20]([CH:25]([C:4]3[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH3:12])=[CH:6][CH:5]=3)[OH:26])=[N:21][C:22]=2[O:23][CH3:24])[CH2:16][CH2:15]1
Reactant: COc1nc(C=O)ccc1C1CC1
Reactant: CCOc1ccc(Br)cc1
Agent: II
Agent: [Mg]
Solvent: C1CCOC1
Product: CCOc1ccc(C(O)c2ccc(C3CC3)c(OC)n2)cc1
Temperature: 50 °C
Reaction time: 1 h
Yield: 86 %

Procedure:
A small amount of iodine was added to a suspension of 1-bromo-4-ethoxybenzene (484 μL) and magnesium (82.3 mg) in THF at room temperature in a nitrogen atmosphere, and the mixture was stirred at 50° C. for one hour. The reaction solution was returned to room temperature and a solution of 5-cyclopropyl-6-methoxypyridine-2-carbaldehyde (300 mg) in tetrahydrofuran (1 mL) was added, followed by stirring at 50° C. for one hour. Tetrahydrofuran was concentrated under reduced pressure and a saturated ammonium chloride solution was added, followed by extraction with ethyl acetate. The organic layer was filtered through diatomaceous earth, and then the solvent was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=50:1→9:1) to give (5-cyclopropyl-6-methoxypyridin-2-yl)(4-ethoxyphenyl)methanol as a yellow oil (438 mg, 86%).
Reaction SMILES: [NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][N:9]2[C:13](=[O:14])[C:12]([CH3:16])([CH3:15])[CH2:11][O:10]2)=[C:4]([Cl:17])[CH:3]=1.[S:18]1[CH:22]=[CH:21][CH:20]=[C:19]1[CH:23]=O>C(O)C>[Cl:17][C:4]1[CH2:3][C:2](=[N:1][CH2:23][C:19]2[S:18][CH:22]=[CH:21][CH:20]=2)[CH:7]=[CH:6][C:5]=1[CH2:8][N:9]1[C:13](=[O:14])[C:12]([CH3:15])([CH3:16])[CH2:11][O:10]1
Reactant: CC1(C)CON(Cc2ccc(N)cc2Cl)C1=O
Reactant: O=Cc1cccs1
Solvent: CCO
Product: CC1(C)CON(CC2=C(Cl)CC(=NCc3cccs3)C=C2)C1=O
Yield: 83.2 %

Procedure:
This compound was prepared in a manner analogous to that of Example 5, using 1.28 grams (0.005 mole) of 2-[(4-amino-2-chlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone and 0.56 gram (0.005 mole) of thiophene-2-carboxaldehyde in 25 mL of ethanol. The reaction mixture was concentrated under reduced pressure to a residual oil. The oil was dissolved in anhydrous diethyl ether and was dried for two hours with magnesium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure to yield 1.46 grams of 2-[[2-chloro-4-[(thien-2-yl)methylimino]phenyl]-methyl]-4,4-dimethyl-3-isoxazolidinone as an oil.
Reaction SMILES: Cl[C:2]1[CH:7]=[C:6]([CH3:8])[N:5]=[C:4]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=2)[N:3]=1.[Cl:15][C:16]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:17]=1[NH2:18]>>[Cl:15][C:16]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][C:17]=1[NH:18][C:2]1[CH:7]=[C:6]([CH3:8])[N:5]=[C:4]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=2)[N:3]=1
Reactant: COc1ccc(Cl)c(N)c1
Reactant: Cc1cc(Cl)nc(-c2ccccn2)n1
Product: COc1ccc(Cl)c(Nc2cc(C)nc(-c3ccccn3)n2)c1

Procedure:
The title compound was prepared from a mixture of 4-chloro-6-methyl-2-(2-pyridinyl)pyrimidine (50 mg, 0.243 mmol) and 2-chloro-5-methoxyaniline (47 mg, 0.243 mmol) similar to Example 13 and isolated as a tan oil (35 mg, 44%). 1H NMR (CDCl3): 8.82–8.80 (m, 1H), 8.47 (d, J=7.8 Hz, 1H), 7.86–7.81 (m, 1H), 7.77 (d, J=2.7 Hz, 1H), 7.41–7.36 (m, 1H), 7.36 (s, 1H), 7.30 (s, 1H), 6.68 (s, 1H), 6.65 (dd, J=2.7, 8.7 Hz, 1H), 3.85 (s, 3H), 2.55 (s, 3H).
Reaction SMILES: [Cl:1][C:2]1[N:7]=[C:6]([CH:8]=[O:9])[CH:5]=[CH:4][CH:3]=1.[CH2:10]([Mg]Br)[CH3:11].C(OCC)C>C1COCC1>[Cl:1][C:2]1[N:7]=[C:6]([CH:8]([OH:9])[CH2:10][CH3:11])[CH:5]=[CH:4][CH:3]=1
Reactant: O=Cc1cccc(Cl)n1
Reactant: CC[Mg]Br
Solvent: CCOCC
Solvent: C1CCOC1
Product: CCC(O)c1cccc(Cl)n1
Temperature: -78 °C
Reaction time: 2 h

Procedure:
To a solution of 6-chloropicolinaldehyde (1.00 g, 7.06 mmol) in 20 mL of THF at −78° C. was added ethylmagnesium bromide, 3.0 M solution in diethyl ether (3.53 mL, 10.60 mmol) slowly. The reaction mixture was stirred at −78° C. for 2 h. The reaction mixture was quenched with sat'd NH4Cl aqueous solution, and extracted with ether (3×100 mL). The combined organic layers were dried over Na2SO4 and evaporated to provide the crude product. The crude product was purified by chromatography on silica gel, eluting with 10 to 60% EtOAc/hexane to provide the title compound. Mass Spectrum (ESI) m/z=172 (M+1).
Reaction SMILES: [Br:1][C:2]1[CH:7]=[C:6](F)[C:5]([N+:9]([O-:11])=[O:10])=[CH:4][C:3]=1[C:12]([F:15])([F:14])[F:13].[NH:16]1[CH:20]=[CH:19][N:18]=[CH:17]1.C(N(CC)C(C)C)(C)C>C(#N)C>[Br:1][C:2]1[C:3]([C:12]([F:15])([F:14])[F:13])=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([N:16]2[CH:20]=[CH:19][N:18]=[CH:17]2)[CH:7]=1
Reactant: O=[N+]([O-])c1cc(C(F)(F)F)c(Br)cc1F
Reactant: c1c[nH]cn1
Solvent: CCN(C(C)C)C(C)C
Solvent: CC#N
Product: O=[N+]([O-])c1cc(C(F)(F)F)c(Br)cc1-n1ccnc1
Temperature: 80 °C
Reaction time: 1.5 h
Yield: 86.2 %

Procedure:
A mixture of 1-bromo-5-fluoro-4-nitro-2-(trifluoromethyl)benzene (16.0 g, 0.0556 mol), imidazole (4.0 g, 0.0588 mol) and N,N-diisopropylethylamine (10.1 mL, 0.0582 mol) in acetonitrile (160 mL) is stirred under nitrogen for 1.5 hour at 80° C. After concentration of the reaction mixture, the residue is partitioned between water and ethyl acetate. The aqueous phase is extracted with ethyl acetate, the combined organic phases are washed in turn with a saturated solution of ammonium chloride, brine and dried over sodium sulfate. Concentration and purification by cake filtration over silica gel, eluting with a mixture of ethyl acetate and cyclohexane from 2/8 to 1/1 affords the title compound as a yellow solid (16.1 g, 86.2%)
Reaction SMILES: [F:1][C:2]1[CH:21]=[CH:20][C:5]2[C:6]([C:9]3[CH:14]=[CH:13][C:12]([O:15][CH2:16][C@@H:17]4[CH2:19][O:18]4)=[CH:11][CH:10]=3)=[N:7][O:8][C:4]=2[CH:3]=1.[NH:22]1[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1>CN(C)C=O.C(O)C>[F:1][C:2]1[CH:21]=[CH:20][C:5]2[C:6]([C:9]3[CH:10]=[CH:11][C:12]([O:15][CH2:16][C@@H:17]([OH:18])[CH2:19][N:22]4[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]4)=[CH:13][CH:14]=3)=[N:7][O:8][C:4]=2[CH:3]=1
Reactant: Fc1ccc2c(-c3ccc(OC[C@@H]4CO4)cc3)noc2c1
Reactant: C1CCNCC1
Solvent: CN(C)C=O
Solvent: CCO
Product: O[C@H](COc1ccc(-c2noc3cc(F)ccc23)cc1)CN1CCCCC1

Procedure:
The title compound is prepared from a mixture of (S)-6-fluoro-3-(4-oxiranylmethoxy-phenyl)-benzo[d]isoxazole in dimethylformamide and piperidine in ethanol essentially as described above in Example 21. Purity by LC/MS=100%, [M+H]+=371.
Reaction SMILES: [Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][CH:3]=1.[CH2:10]([O:12][C:13](=[O:20])[CH:14]=[C:15]([NH2:19])[O:16][CH2:17][CH3:18])[CH3:11]>>[CH2:10]([O:12][C:13]([C:14]1[CH:6]([C:5]2[CH:8]=[CH:9][C:2]([Cl:1])=[CH:3][CH:4]=2)[CH:14]([C:13]([O:12][CH2:10][CH3:11])=[O:20])[C:15]([O:16][CH2:17][CH3:18])=[N:19][C:15]=1[NH2:19])=[O:20])[CH3:11]
Reactant: O=Cc1ccc(Cl)cc1
Reactant: CCOC(=O)C=C(N)OCC
Product: CCOC(=O)C1=C(N)N=C(OCC)C(C(=O)OCC)C1c1ccc(Cl)cc1
Yield: 56 %

Procedure:
Boiling a solution of 7.1 g of 4-chlorobenzaldehyde and 15.9 g of 3-amino-3-ethoxyacrylic acid ethyl ester in 50 ml of alcohol for 8 hours yields 2-amino-4-(4-chlorophenyl)-6-ethoxy-4,5-dihydropyridine-3,5-dicarboxylic acid diethyl ester of melting point 130°-132° C (ethyl acetate/petroleum ether). Yield: 56% of theory.
Reaction SMILES: [F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH2:9].N1C=CC=CC=1.[CH3:16][O:17][C:18]1[CH:19]=[C:20]([S:24](Cl)(=[O:26])=[O:25])[CH:21]=[CH:22][CH:23]=1.Cl>C(Cl)Cl>[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH:9][S:24]([C:20]1[CH:21]=[CH:22][CH:23]=[C:18]([O:17][CH3:16])[CH:19]=1)(=[O:26])=[O:25]
Reactant: COc1cccc(S(=O)(=O)Cl)c1
Reactant: Nc1ccc(F)cc1F
Agent: Cl
Solvent: c1ccncc1
Solvent: ClCCl
Product: COc1cccc(S(=O)(=O)Nc2ccc(F)cc2F)c1
Reaction time: 12 h

Procedure:
To 2,4-difluoro-phenylamine(42, 0.44 mL, 4.4 mmol) in methylene chloride (10.0 mL), under an atmosphere of nitrogen, were added pyridine (1.00 mL, 12.4 mmol) and 3-methoxy-benzenesulfonyl chloride (1.00 g, 4.84 mmol). After 12 hours, the reaction was poured into cold 1 M HCl and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated and purified by silica gel column chromatography eluting with 20% ethyl acetate in hexane to give light yellow solid (91, 0.90 g, 69%). MS (ESI) [M+H+]+=300.
Reaction SMILES: [NH:1]1[CH2:6][CH2:5][C:4]2([C:14]3[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:8](=[O:15])[O:7]2)[CH2:3][CH2:2]1.C(=O)(O)[O-].[Na+].[CH2:21](Br)[CH:22]=[CH2:23]>C(Cl)(Cl)Cl>[CH2:23]([N:1]1[CH2:6][CH2:5][C:4]2([C:14]3[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:8](=[O:15])[O:7]2)[CH2:3][CH2:2]1)[CH:22]=[CH2:21]
Reactant: O=C1OC2(CCNCC2)c2ccccc21
Reactant: C=CCBr
Agent: O=C([O-])O
Agent: [Na+]
Solvent: ClC(Cl)Cl
Product: C=CCN1CCC2(CC1)OC(=O)c1ccccc12

Procedure:
A mixture of 1.02 g. of 1,3-dihydrospiro[isobenzofuran-1,4'-piperidine]-3-one, 1.0 g. of sodium bicarbonate, 10 ml. of chloroform, and 0.60 g. of allyl bromide is stirred at room temperature for 24 hours and filtered. The filtrate is washed with water, dried over potassium carbonate, and concentrated to an oily solid.
Reaction SMILES: [CH2:1]([O:8][CH:9]([CH2:12][O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH2:10][OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[S:32](Cl)([C:35]1[CH:41]=[CH:40][C:38]([CH3:39])=[CH:37][CH:36]=1)(=[O:34])=[O:33]>N1C=CC=CC=1>[CH2:1]([O:8][CH:9]([CH2:12][O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])[CH2:10][O:11][S:32]([C:35]1[CH:41]=[CH:40][C:38]([CH3:39])=[CH:37][CH:36]=1)(=[O:34])=[O:33])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
Reactant: Cc1ccc(S(=O)(=O)Cl)cc1
Reactant: CCCCCCCCCCCCCCCCCCOCC(CO)OCc1ccccc1
Solvent: c1ccncc1
Product: CCCCCCCCCCCCCCCCCCOCC(COS(=O)(=O)c1ccc(C)cc1)OCc1ccccc1
Temperature: 25 °C
Reaction time: 8 h
Yield: 88.6 %

Procedure:
In 5 ml of pyridine were dissolved 1 g (2.3 mmole) of 2-O-benzyl-3-O-octadecylglycerol and 1.144 g (6.0 mmole) of tosyl chloride, and the solution was stirred at room temperature overnight. The reaction solution was concentrated to dryness under reduced pressure, and 20 ml of 10% aqueous hydrogencarbonate solution and 20 ml of ether were added to the residue, followed by shaking thoroughly. The ether layer was separated, dried over sodium sulfate and concentrated to dryness under reduced pressure. The residue was purified by 15 g of silica gel, with n-hexane-ethyl acetate (9:1) used as an eluent, to give 1.2 g (yield of 88.6%) of a colorless solid.
Reaction SMILES: O.[OH-].[Li+].[CH2:4]([O:11][C:12]1[CH:13]=[C:14]([CH:19]=[C:20]([O:22][C@@H:23]([CH3:36])[CH2:24][O:25][Si:26]([CH:33]([CH3:35])[CH3:34])([CH:30]([CH3:32])[CH3:31])[CH:27]([CH3:29])[CH3:28])[CH:21]=1)[C:15]([O:17]C)=[O:16])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>O.C1COCC1>[CH2:4]([O:11][C:12]1[CH:13]=[C:14]([CH:19]=[C:20]([O:22][C@@H:23]([CH3:36])[CH2:24][O:25][Si:26]([CH:30]([CH3:32])[CH3:31])([CH:27]([CH3:29])[CH3:28])[CH:33]([CH3:35])[CH3:34])[CH:21]=1)[C:15]([OH:17])=[O:16])[C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1
Reactant: COC(=O)c1cc(OCc2ccccc2)cc(O[C@@H](C)CO[Si](C(C)C)(C(C)C)C(C)C)c1
Agent: [Li+]
Agent: [OH-]
Solvent: C1CCOC1
Solvent: O
Product: CC(C)[Si](OC[C@H](C)Oc1cc(OCc2ccccc2)cc(C(=O)O)c1)(C(C)C)C(C)C
Temperature: 43 °C
Reaction time: 16 h
Yield: 100.2 %

Procedure:
Lithium hydroxide monohydrate (12.14 g, 0.289 mol) in water (100 mL) was added to a solution of methyl 3-(benzyloxy)-5-{(1S)-1-methyl-2-[(triisopropylsilyl)oxy]ethoxy}benzoate (62 g, 0.131 mol) in THF (300 mL) and warmed to 43° C. The reaction was stirred for 16 hours, the THF removed in vacuo and the resultant mixture acidified to pH 5 with 10% w/v citric acid. This was extracted with ethyl acetate (2×300 mL) and the combined organic layers were dried (MgSO4), filtered and evaporated to afford the title compound (60.2 g).