Azzindani/Open_Reaction_Data huggingface dataset:
Reaction SMILES: Br[CH:2]1[C:10]2[C:5](=[CH:6][C:7]([Cl:11])=[CH:8][CH:9]=2)[C:4](=[O:12])[CH2:3]1.C(N(CC)CC)C>O1CCCC1>[Cl:11][C:7]1[CH:6]=[C:5]2[C:10]([CH:2]=[CH:3][C:4]2=[O:12])=[CH:9][CH:8]=1
Reactant: O=C1CC(Br)c2ccc(Cl)cc21
Solvent: CCN(CC)CC
Solvent: C1CCOC1
Product: O=C1C=Cc2ccc(Cl)cc21
Temperature: 2.5 °C
Reaction time: 2 h
Yield: 26.9 %

Procedure:
13.4 kg 3-Bromo-6-chloro-indan-1-one (A; for references on this material, see: Bøgesø EP 35363 A1 19810909 and Kehler, Juhl, Püschl, WO 2008025361; each herein incorporated by reference in its entirety) was dissolved in tetrahydrofuran (170.8 L), and the solution was cooled to 0-5° C. (Scheme 9). Triethylamine (9.1 L) was added over 0.5 h. The mixture was stirred at 0-5° C. for 5 hours before an additional portion of triethylamine (2.48 L) was added over 0.5 hour, and stirring was continued for 2 hours. The mixture was filtered, and the filtrate was concentrated to 30 L before n-heptane (102 L) was added. The volume was reduced to 60 L. More n-heptane (203 L) was added, and the mixture was stirred for 1 hour. Silica gel (17.2 kg) was added. The mixture was filtered, and the residual solid was washed with n-heptane (100 L). The combined filtrates were concentrated to 30 L and stirred at 0-5° C. for 1 hour. The mixture was centrifuged, and the residual solid was dried to afford 6-chloro-inden-1-one (compound B; 2.42 kg) sufficiently pure for the next step.
Reaction SMILES: [OH:1][C:2]1[C:9]([OH:10])=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].C(=O)([O-])[O-].[K+].[K+].I[CH2:18][CH2:19][CH3:20].O>CN(C=O)C>[OH:10][C:9]1[C:2]([O:1][CH2:18][CH2:19][CH3:20])=[C:3]([CH:6]=[CH:7][CH:8]=1)[CH:4]=[O:5]
Reactant: CCCI
Reactant: O=Cc1cccc(O)c1O
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: O
Solvent: CN(C)C=O
Product: CCCOc1c(O)cccc1C=O
Yield: 42.3 %

Procedure:
2,3-Dihydroxybenzaldehyde (1.16 g, 8.40 mmol), potassium carbonate (1.16 g, 8.40 mmol) and 1-iodopropane (0.82 mL, 1.43 g, 8.40 mmol) in dry DMF (10 mL) were stirred at ambient temperature for 20 h. The reaction mixture was poured into water and extracted with diethyl ether. The diethyl ether layer was washed with water (2×), then extracted with 1N sodium hydroxide solution (3×). The basic extracts were combined and acidified by addition of 3N hydrochloric acid, then extracted with diethyl ether. The ether layer was washed with 10% sodium hydrogen carbonate (3×), water (1×), brine (1×), and dried over MgSO4. After filtration, the solvent was removed in vacuo to yield 3-hydroxy-2-propoxybenzaldehyde (0.64 g, 42%) as a yellow solid.
Reaction SMILES: [C:1]([C:4]1[C:9]2[CH2:10][C:11](=O)[C:12]3[CH:18]=[CH:17][CH:16]=[C:15](F)[C:13]=3[S:14][C:8]=2[CH:7]=[CH:6][CH:5]=1)([OH:3])=[O:2].[OH2:21].NN>C(O)C.O1CCOCC1>[C:1]([C:4]1[C:9]2[CH2:10][CH2:11][C:12]3[CH:18]=[CH:17][CH:16]=[C:15]([OH:21])[C:13]=3[S:14][C:8]=2[CH:7]=[CH:6][CH:5]=1)([OH:3])=[O:2]
Reactant: O=C(O)c1cccc2c1CC(=O)c1cccc(F)c1S2
Reactant: O
Agent: NN
Solvent: C1COCCO1
Solvent: CCO
Product: O=C(O)c1cccc2c1CCc1cccc(O)c1S2
Reaction time: 2 h
Yield: 12.7 %

Procedure:
5.0g of 9-carboxy-4-fluoro-10,11-dihydrodibenzo[b,f]thiepin-11-one and 5.0g of 100% hydrazine hydrate were dissolved in the mixed solvent of 50ml of ethanol and 50ml of dioxane. The resulting mixture was heated under reflux for 5 hours. The solvent was evaporated under reduced pressure to obtain the residue, which was washed with ethanol. To this was added 5.0g of sodium hydroxide in 100ml of diethylene glycol and the resulting mixture was heated with stirring at 180°-200° C for 2 hours. After cooling, water was added to the mixture, which was extracted with benzene. The aqueous layer was acidified with hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was evaporated to obtain a glutinous residue which was chromatographed over silica gel, and eluted with benzene-ethyl acetate (1:1). Recrystallization of the thus obtained crude product from methanol-water afforded 600mg of 9-carboxy-4-hydroxy-10,11-dihydrodibenzo-[b,f]thiepin having a melting point of 171°-173° C.
Reaction SMILES: [F:1][C:2]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[CH:3][CH3:4].Br[N:12]1C(=O)CC[C:13]1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[Na+].[Cl-].[C-]#N.[Na+]>C(Cl)(Cl)(Cl)Cl.CN(P(N(C)C)(N(C)C)=O)C.O.CCOCC.CCCCCC.CCCCCC>[F:1][C:2]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[CH:3][CH2:4][C:13]#[N:12]
Reactant: CC=C(F)c1ccccc1
Reactant: O=C1CCC(=O)N1Br
Agent: O=C(OOC(=O)c1ccccc1)c1ccccc1
Agent: [C-]#N
Agent: [Cl-]
Solvent: O
Solvent: CN(C)P(=O)(N(C)C)N(C)C
Solvent: ClC(Cl)(Cl)Cl
Product: N#CCC=C(F)c1ccccc1
Reaction time: 8 h

Procedure:
To 1.36 g (10 mmol) of α-fluoro-β-methylstyrene in 20 ml of CCl4 is added 1.78 g (10 mmol) of N-bromosuccinimide and 50 g of dibenzoyl peroxide. The reaction is stirred overnight and then poured into hexane and water. The hexane layer is shaken against sat. NaCl solution and dried (Na2SO4). The product bromide after solvent removal is dissolved in 10 ml of THF and 10 ml of HMPT, and 1.96 g (40 mmol) of sodium cyanide is added. The reaction is warmed to 60° and after 24 hours poured into ether/hexane (2:8) and water. The organic phase is washed several times with water, dried, and solvent removed to give 4-fluoro-4-phenyl-3-butenonitrile.
Reaction SMILES: [F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:13])=[C:6]([C:8]([CH3:12])([CH3:11])[C:9]#N)[CH:7]=1.[H-].C([Al+]CC(C)C)C(C)C.C(OCC)(=[O:26])C>C1(C)C=CC=CC=1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:13])=[C:6]([C:8]([CH3:12])([CH3:11])[CH:9]=[O:26])[CH:7]=1
Reactant: CCOC(C)=O
Reactant: Cc1ccc(F)cc1C(C)(C)C#N
Agent: CC(C)C[Al+]CC(C)C
Agent: [H-]
Solvent: Cc1ccccc1
Product: Cc1ccc(F)cc1C(C)(C)C=O
Temperature: 25 °C
Reaction time: 4 h

Procedure:
6.1 g of 2-(5-fluoro-2-methylphenyl)-2-methylpropionitrile, dissolved in 60 ml of toluene, is mixed at −70° C. for 45 minutes with 44 ml of 1.2 M diisobutylaluminum hydride solution in toluene. After 4 hours at −78° C., 120 ml of ethyl acetate is added in drops. It is heated to room temperature and washed three times with 2N sulfuric acid and once with water. The ethyl acetate phase is dried (Na2SO4) and concentrated by evaporation. After distillation, 5.3 g of 2-(5-fluoro-2-methylphenyl)-2-methylpropionaldehyde of boiling point 120° C./0.031 hPa is obtained.
Reaction SMILES: Cl[C:2]([O:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:3].[CH3:11][C@H:12]1[CH2:17][O:16][CH2:15][CH2:14][N:13]1[C:18]1[CH:23]=[C:22]([CH2:24][S:25]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][C:29]=2[C:34]([F:37])([F:36])[F:35])(=[O:27])=[O:26])[N:21]=[C:20]([C:38]2[CH:44]=[CH:43][C:41]([NH2:42])=[CH:40][CH:39]=2)[N:19]=1.C(=O)([O-])O.[Na+]>O1CCOCC1.C(OCC)(=O)C>[CH3:11][C@H:12]1[CH2:17][O:16][CH2:15][CH2:14][N:13]1[C:18]1[CH:23]=[C:22]([CH2:24][S:25]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][C:29]=2[C:34]([F:35])([F:36])[F:37])(=[O:27])=[O:26])[N:21]=[C:20]([C:38]2[CH:39]=[CH:40][C:41]([NH:42][C:2](=[O:3])[O:4][C:5]3[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=3)=[CH:43][CH:44]=2)[N:19]=1
Reactant: O=C(Cl)Oc1ccccc1
Reactant: C[C@H]1COCCN1c1cc(CS(=O)(=O)c2ccccc2C(F)(F)F)nc(-c2ccc(N)cc2)n1
Agent: O=C([O-])O
Agent: [Na+]
Solvent: CCOC(C)=O
Solvent: C1COCCO1
Product: C[C@H]1COCCN1c1cc(CS(=O)(=O)c2ccccc2C(F)(F)F)nc(-c2ccc(NC(=O)Oc3ccccc3)cc2)n1
Temperature: 25 °C
Reaction time: 2 h
Yield: 97.7 %

Procedure:
Phenyl chloroformate (0.535 mL, 4.26 mmol) was added to 4-[4-[(3S)-3-methylmorpholin-4-yl]-6-[[2-(trifluoromethyl)phenyl]sulfonylmethyl]pyrimidin-2-yl]aniline (1.4 g, 2.84 mmol) and sodium hydrogen carbonate (0.358 g, 4.26 mmol) in dioxane (20 mL) at 5° C. under nitrogen. The resulting mixture was stirred at RT for 2 hours then the reaction mixture diluted with ethyl acetate (200 mL), and washed with water (125 mL). The organic layer was dried (MgSO4), filtered and evaporated to afford crude product which was triturated with a mixture of diethyl ether and isohexane to give the desired material as a white solid (1.70 g).
Reaction SMILES: [C:1]([NH:4][C:5]1[CH:6]=[C:7]([C:11]#[CH:12])[CH:8]=[CH:9][CH:10]=1)(=[O:3])[CH3:2]>C(O)(=O)C>[C:1]([NH:4][C:5]1[CH:6]=[C:7]([CH:11]=[CH:12][C:12]#[C:11][C:7]2[CH:8]=[CH:9][CH:10]=[C:5]([NH:4][C:1](=[O:3])[CH3:2])[CH:6]=2)[CH:8]=[CH:9][CH:10]=1)(=[O:3])[CH3:2]
Reactant: C#Cc1cccc(NC(C)=O)c1
Solvent: CC(=O)O
Product: CC(=O)Nc1cccc(C#CC=Cc2cccc(NC(C)=O)c2)c1
Temperature: 25 °C
Yield: 96.3 %

Procedure:
To 350 ml of deoxygenated acetic acid was added 1.4 g of cuprous acetate whereupon a clear blue solution formed. The solution was brought to reflux, under nitrogen, and 14.35 g (0.09 mole) of 3-acetamidophenylacetylene was added as a solid. The reaction mixture was maintained at reflux for 12 hours and cooled to room temperature. Isolation of the material was carried out by precipitation of the reaction mixture into distilled water and collection by filtration. The light tan material was air dried and recrystallized from isopropanol to give 13.8 g of product (96% yield) (m.p. 276°-278° C.).
Reaction SMILES: [CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([SH:9])=[CH:5][CH:4]=1.C(N(CC)CC)C.[C:17]([O:21][C:22]([N:24]1[CH2:28][CH2:27][CH2:26][C@H:25]1[CH:29]1[O:31][CH2:30]1)=[O:23])([CH3:20])([CH3:19])[CH3:18]>CO>[C:17]([O:21][C:22]([N:24]1[CH2:28][CH2:27][CH2:26][C@H:25]1[CH:29]([OH:31])[CH2:30][S:9][C:6]1[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=1)=[O:23])([CH3:20])([CH3:19])[CH3:18]
Reactant: COc1ccc(S)cc1
Reactant: CC(C)(C)OC(=O)N1CCC[C@H]1C1CO1
Solvent: CO
Solvent: CCN(CC)CC
Product: COc1ccc(SCC(O)[C@@H]2CCCN2C(=O)OC(C)(C)C)cc1
Reaction time: 1.5 h

Procedure:
4-Methoxythiophenol (1.0 ml) and triethylamine (1.0 ml) were added to (2S)-1-(t-butoxycarbonyl)-2-(1,2-epoxyethyl)-pyrrolidine (1.57 g) as obtained in Example 1-A) in methanol (50 ml), and the mixture was stirred for 1.5 hours under reflux. The reaction mixture was concentrated and the residue was poured into ice-water, followed by extraction with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate and concentrated. The residue was recrystallized from a mixted solution of hexane-ethyl acetate to give 2.16 g of the title compound as colorless needles.
Reaction SMILES: [N:1]1([CH2:6][CH2:7][N:8]2[C:16]3[C:11](=[CH:12][C:13]([NH2:17])=[CH:14][CH:15]=3)[CH:10]=[N:9]2)[CH2:5][CH2:4][CH2:3][CH2:2]1.[O:18]([C:25]1[CH:30]=[CH:29][C:28]([CH2:31][C:32](O)=[O:33])=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>>[O:18]([C:25]1[CH:26]=[CH:27][C:28]([CH2:31][C:32]([NH:17][C:13]2[CH:12]=[C:11]3[C:16](=[CH:15][CH:14]=2)[N:8]([CH2:7][CH2:6][N:1]2[CH2:5][CH2:4][CH2:3][CH2:2]2)[N:9]=[CH:10]3)=[O:33])=[CH:29][CH:30]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1
Reactant: O=C(O)Cc1ccc(Oc2ccccc2)cc1
Reactant: Nc1ccc2c(cnn2CCN2CCCC2)c1
Product: O=C(Cc1ccc(Oc2ccccc2)cc1)Nc1ccc2c(cnn2CCN2CCCC2)c1

Procedure:
1-(2-pyrrolidin-1-yl-ethyl)-1H-indazol-5-ylamine and (4-phenoxy-phenyl)-acetic acid were processed as described in Example 17 to provide the title compound. MS (DCI/NH3) MS m/z 441 (M+H)+; 1H NMR (500 MHz, DMSO-d6) δ ppm 1.83 (m, 2 H), 1.99 (m, 2 H), 3.05 (m, 2 H), 3.52 (m, 2 H), 3.65 (s, 2 H), 3.71 (q, J=5.93 Hz, 2 H), 4.74 (t, J=6.24 Hz, 2 H), 6.99 (m, 4 H), 7.13 (m, 1 H), 7.37 (m, 4 H), 7.54 (m, 1 H), 7.69 (m, 1 H), 8.14 (m, 2 H), 9.63 (br s, N H).
Reaction SMILES: [CH3:1][C:2]1[NH:3][CH:4]=[C:5]([C:7]#[C:8][C:9]2[CH:10]=[C:11]([CH:14]=[CH:15][CH:16]=2)[C:12]#[N:13])[N:6]=1.[F:17][C:18]1[CH:19]=[N:20][CH:21]=[C:22](F)[CH:23]=1>>[F:17][C:18]1[CH:23]=[C:22]([N:3]2[CH:4]=[C:5]([C:7]#[C:8][C:9]3[CH:10]=[C:11]([CH:14]=[CH:15][CH:16]=3)[C:12]#[N:13])[N:6]=[C:2]2[CH3:1])[CH:21]=[N:20][CH:19]=1
Reactant: Cc1nc(C#Cc2cccc(C#N)c2)c[nH]1
Reactant: Fc1cncc(F)c1
Product: Cc1nc(C#Cc2cccc(C#N)c2)cn1-c1cncc(F)c1

Procedure:
The title compound, MS: m/e=303.5 (M+), was prepared in accordance with the general method of example 1 from 3-(2-methyl-1H-imidazol-4-ylethynyl)-benzonitrile and 3,5-difluoro-pyridine.
Reaction SMILES: [CH3:1][C:2]1([CH3:19])[C:11]2[C:6](=[CH:7][C:8](Br)=[CH:9][CH:10]=2)[N:5]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:4][CH2:3]1.C(N(CC)CC)C.[CH3:27][Si:28]([C:31]#[CH:32])([CH3:30])[CH3:29].[Cl-]>[Cu]I.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(Cl)Cl>[CH3:1][C:2]1([CH3:19])[C:11]2[C:6](=[CH:7][C:8]([C:32]#[C:31][Si:28]([CH3:30])([CH3:29])[CH3:27])=[CH:9][CH:10]=2)[N:5]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:4][CH2:3]1
Reactant: CC1(C)CCN(c2ccccc2)c2cc(Br)ccc21
Reactant: C#C[Si](C)(C)C
Agent: [Cu]I
Agent: c1ccc([P]([Pd][P](c2ccccc2)(c2ccccc2)c2ccccc2)(c2ccccc2)c2ccccc2)cc1
Agent: [Cl-]
Solvent: CCN(CC)CC
Solvent: ClCCl
Product: CC1(C)CCN(c2ccccc2)c2cc(C#C[Si](C)(C)C)ccc21
Temperature: 70 °C

Procedure:
To a solution of 0.10 g (0.32 mmol) of 4,4-dimethyl-1,2,3,4-tetrahydro-N-phenyl-7-bromoquinoline (Compound 6) and 5.0 g (4.0 mL, 36 mmol) triethylamine were added 0.032 g (0.17 mmol) of copper(I) iodide, 0.70 g (1.0 mL, 7.1 mmol) of (trimethylsilyl)acetylene, and 0.050 g (0.07 mmol) of bis(triphenylphosphine)palladium(ID chloride. The resulting mixture was heated at 70° C. for 22 hours. The reaction was cooled, methylene chloride was added, and the mixture was adsorbed onto silica gel. The mixture was purified by flash chromatography (hexanes) to give the title compound as a yellow solid. PNMR (300 MHz, CDCl3) d 0.17 (9 H, s), 1.32 (6 H, s), 1.82 (2 H, t, J=6.0 Hz), 3.61 (2 H, t, J=6.0 Hz), 6.85 (2 H, overlapping d's), 7.15-7.41 (6 H, m).
Reaction SMILES: [H-].[Al+3].[Li+].[H-].[H-].[H-].[CH3:7][C:8]1[CH:17]=[CH:16][C:11]([C:12](OC)=[O:13])=[CH:10][C:9]=1[C@H:18]1[C@H:23]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@@H:22]([O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C@H:21]([O:40][CH2:41][C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[C@@H:20]([CH2:48][O:49][CH2:50][C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[O:19]1.O>C1COCC1>[CH2:25]([O:24][C@@H:23]1[C@@H:22]([O:32][CH2:33][C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)[C@H:21]([O:40][CH2:41][C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[C@@H:20]([CH2:48][O:49][CH2:50][C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[O:19][C@H:18]1[C:9]1[CH:10]=[C:11]([CH2:12][OH:13])[CH:16]=[CH:17][C:8]=1[CH3:7])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1
Reactant: COC(=O)c1ccc(C)c([C@@H]2O[C@H](COCc3ccccc3)[C@@H](OCc3ccccc3)[C@H](OCc3ccccc3)[C@H]2OCc2ccccc2)c1
Agent: [Al+3]
Agent: [H-]
Agent: [Li+]
Solvent: C1CCOC1
Solvent: O
Product: Cc1ccc(CO)cc1[C@@H]1O[C@H](COCc2ccccc2)[C@@H](OCc2ccccc2)[C@H](OCc2ccccc2)[C@H]1OCc1ccccc1
Reaction time: 1 h
Yield: 80.3 %

Procedure:
Lithium aluminum hydride (73 mg) was added to a solution of methyl 4-methyl-3-[(2S,3S,4R,5R,6R)-3,4,5-tris(benzyloxy)-6-[(benzyloxy)methyl]tetrahydro-2H-pyran-2-yl]benzoate (1.3 g) in THF (10 ml) at 0° C. and the mixture was stirred for one hour. The reaction mixture was poured into ice-cooled water and the insoluble matter was separated by filtration. The filtrate was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated. The residue was purified by silica gel column chromatography (n-hexane-ethyl acetate) to obtain (1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-[5-(hydroxymethyl)-2-methylphenyl]-D-glucitol (1.0 g).
Reaction SMILES: [NH2:1][CH2:2][CH2:3][CH2:4][Si:5]([CH3:12])([O:9][CH2:10]C)[O:6][CH2:7]C.C(N)C=C.C[Si](C)(C)N(CC=C)[Si](C)(C)C.C[SiH](OC)OC>[Pt].CO>[NH2:1][CH2:2][CH2:3][CH2:4][Si:5]([CH3:12])([O:9][CH3:10])[O:6][CH3:7]
Reactant: CCO[Si](C)(CCCN)OCC
Agent: [Pt]
Agent: C=CCN([Si](C)(C)C)[Si](C)(C)C
Agent: CO[SiH](C)OC
Solvent: C=CCN
Solvent: CO
Product: CO[Si](C)(CCCN)OC

Procedure:
There is considerable prior art relating to the synthesis of poly(aminoalkylmethylsiloxanes). Generally, poly(aminoalkylmethylsiloxanes) have been produced by first preparing aminoalkylmethyldialkoxysilanes, followed by hydrolysis with or without an endblocking agent, such as a trimethylsilyl derivative, to form cyclic and linear poly(3-aminoalkylmethylsiloxanes). The isomeric purity of the poly(aminoalkylmethylsiloxane) fluids, prepared in the manner of the prior art, is dependent upon the isomeric purity of the aminoalkylmethyldialkoxysilane prepared in the first step of the synthesis. German Patent No. 2408480 describes the reaction of a silazane derivative from allylamine and an organohydrochlorosilane, in the presence of a proton acceptor to form an intermediate silazane which then undergoes a hydrosilylation reaction catalyzed by a platinum catalyst. Upon alcoholysis, the intermediate hydrosilylation product forms 3-aminopropylmethyldiethoxysilane in 70% overall yield. A molar excess of at least 50% of allylamine is used in this process. Identification of the beta-isomer in the product was not made. Japanese Patent No. 10017578 describes another method of synthesis by hydrosilylation of N,N-bis(trimethylsilyl)allylamine by methyldimethoxysilane. The product of that reaction is then heated with methanol to form 3-aminopropylmethyldimethoxysilane in at least 85% overall yield. The presence of the beta-isomer in the product was not made. Japanese Patent No. 11209384 describes the use of a rhodium:cyclooctadiene complex as a hydrosilylation catalyst for the addition of methyldiethoxysilane to allylamine to form 3-aminopropylmethyldiethoxysilane in 78% yield. 2-Aminopropylmethyldiethoxysilane is formed at very low levels in this process not exceeding 0.5%. U.S. Pat. No. 5,391,675 describes the formation of an aminopropylmethylsiloxy-containing polydimethylsiloxane by barium or strontium hydroxide catalyzed condensation of a silanol terminated polydimethylsiloxane with a 3-aminopropylalkoxysilane with elimination of an alcohol.
Reaction SMILES: [C:1]1([C@H:7]2[N:21]3[C:22]4[C:14]([C:15]5[C:16](=[O:23])[CH2:17][CH2:18][CH2:19][C:20]=53)=[CH:13][CH:12]=[CH:11][C:10]=4[O:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[Li+].[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>CN(C=O)C.C(OCC)(=O)C.O>[C:1]1([C@H:7]2[N:21]3[C:22]4[C:14]([C:15]5[C:20]3=[CH:19][CH:18]=[CH:17][C:16]=5[OH:23])=[CH:13][CH:12]=[CH:11][C:10]=4[O:9][CH2:8]2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1
Reactant: O=C1CCCc2c1c1cccc3c1n2[C@H](c1ccccc1)CO3
Agent: O=C([O-])[O-]
Agent: [Br-]
Agent: [Cl-]
Solvent: O
Solvent: CN(C)C=O
Solvent: CCOC(C)=O
Product: Oc1cccc2c1c1cccc3c1n2[C@H](c1ccccc1)CO3
Temperature: 60 °C
Yield: 34.7 %

Procedure:
To (R)-(−)-1-phenyl-1,2,9,10-tetrahydro[1,4]oxazino[2,3,4-jk]carbazol-7(8H)-one (17.3 g, 57.3 mmol) in dry DMF (60 mL) is added anhydrous cupric chloride (17.7 g, 131.8 mmol) and anhydrous lithium chloride (9.6 g, 229 mmol). The mixture is heated at 60° C. for 40 h. The mixture is then poured into water (600 mL), forming solids. The solids are dissolved in ethyl acetate (50 mL) and filtered to remove inorganic solids. The filtrates are concentrated to dryness and the resulting solids are dissolved in DMF (60 mL), to which is added lithium bromide (12.4 g, 143 mmol) and lithium carbonate (10.6 g, 143 mmol). The mixture is heated at 120° C. for 6 h, cooled, then partitioned between water and CH2Cl2, and the organic layer washed three times with water (200 mL). Column chromatography (600 mL silica) is performed using EtOAc/hexanes (20/80) as eluent. The material is then rechromatographed (600 mL silica) using EtOAc/hexane (20/80) as eluent to give 6.0 g (35%) of (R)-(−)-1-phenyl-1,2-dihydro[1,4]oxazino[2,3,4-jk]carbazol-7-ol; [□]25D=−121° (c 0.73, methylene chloride).
Reaction SMILES: [CH2:1]([C:3]1[C:8]([B:9]2[O:13][C:12]([CH3:15])([CH3:14])[C:11]([CH3:17])([CH3:16])[O:10]2)=[CH:7][CH:6]=[CH:5][C:4]=1[CH:18]1[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]1)[CH3:2].Br[CH2:25][CH2:26][CH2:27][C:28]([O:30][CH2:31][CH3:32])=[O:29].C(=O)([O-])[O-].[K+].[K+].C(OCC)(=O)C>CN(C)C=O>[CH2:1]([C:3]1[C:8]([B:9]2[O:10][C:11]([CH3:17])([CH3:16])[C:12]([CH3:14])([CH3:15])[O:13]2)=[CH:7][CH:6]=[CH:5][C:4]=1[CH:18]1[CH2:23][CH2:22][N:21]([CH2:25][CH2:26][CH2:27][C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH2:20][CH2:19]1)[CH3:2]
Reactant: CCOC(=O)CCCBr
Reactant: CCc1c(B2OC(C)(C)C(C)(C)O2)cccc1C1CCNCC1
Agent: O=C([O-])[O-]
Agent: [K+]
Solvent: CCOC(C)=O
Solvent: CN(C)C=O
Product: CCOC(=O)CCCN1CCC(c2cccc(B3OC(C)(C)C(C)(C)O3)c2CC)CC1
Temperature: 60 °C
Yield: 48.9 %

Procedure:
To a solution of 4-[2-ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]piperidine (D119) (300 mg, 0.952 mmol) in N,N-Dimethylformamide (DMF) (10 mL) was added ethyl 4-bromobutanoate (0.272 mL, 1.903 mmol) and potassium carbonate (526 mg, 3.81 mmol). The reaction solution was heated to 60° C. overnight. Ethyl acetate was added and the resulting solution was washed with water, brine. The organic layer was dried over anhydrous Na2SO4 and concentrated to afford ethyl 4-{4-[2-ethyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1-piperidinyl}butanoate (D121) (200 mg). MS (ES): C25H40BNO4 requires 429.3. found 430.1 (M+H+).
Reaction SMILES: [CH:1]1([C@@H:6]([C:20]2[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=2)[C:7]([O:9][C@@H]2C[C@H](C)CC[C@H]2C(C)C)=[O:8])[CH2:5][CH2:4][CH2:3][CH2:2]1>FC(F)(F)C(O)=O>[CH:1]1([C@@H:6]([C:20]2[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=2)[C:7]([OH:9])=[O:8])[CH2:5][CH2:4][CH2:3][CH2:2]1
Reactant: Cc1ccc([C@@H](C(=O)O[C@@H]2C[C@H](C)CC[C@H]2C(C)C)C2CCCC2)cc1
Solvent: O=C(O)C(F)(F)F
Product: Cc1ccc([C@@H](C(=O)O)C2CCCC2)cc1

Procedure:
50.0 g (0.140 mol) of (1R,2S,5R)-5-methyl-2-(propan-2-yl)cyclohexyl(2S)-cyclopentyl(4-methylphenyl)ethanoate were stirred under reflux for 16 h in 500 ml of trifluoroacetic acid. The trifluoroacetic acid was then removed on a rotary evaporator and the residue was taken up in 500 ml each of water and ethyl acetate. After extraction, the organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate and concentrated. The residue was taken up in 1.5 liters of water, adjusted to pH 10 with aqueous sodium hydroxide solution and washed twice with in each case 300 ml of tert-butyl methyl ether. The aqueous phase was then adjusted to pH 4 using concentrated hydrochloric acid and extracted twice with in each case 300 ml of ethyl acetate. The combined ethyl acetate extracts were dried over sodium sulfate, filtered and concentrated on a rotary evaporator. This gave 27.4 g (89% of theory) of the title compound.
Reaction SMILES: Cl.[CH3:2][O:3][C:4](=[O:22])[C@H:5]([CH2:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[O:20][CH3:21])=[CH:10][CH:9]=1)[NH2:6].[C:23]1([C@H:29]([CH3:33])[C:30](O)=[O:31])[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.C1C=CC2N(O)N=NC=2C=1.CCN(C(C)C)C(C)C>CN(C=O)C.C(Cl)CCl>[CH3:2][O:3][C:4](=[O:22])[C@H:5]([CH2:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[O:20][CH3:21])=[CH:10][CH:9]=1)[NH:6][C:30](=[O:31])[C@H:29]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[CH3:33]
Reactant: C[C@H](C(=O)O)c1ccccc1
Reactant: COC(=O)[C@@H](N)Cc1ccc(-c2ccccc2OC)cc1
Agent: Cl
Agent: On1nnc2ccccc21
Solvent: CN(C)C=O
Solvent: CCN(C(C)C)C(C)C
Solvent: ClCCCl
Product: COC(=O)[C@H](Cc1ccc(-c2ccccc2OC)cc1)NC(=O)[C@@H](C)c1ccccc1
Temperature: 25 °C
Reaction time: 18 h
Yield: 79.6 %

Procedure:
A mixture of 4-(2-methoxyphenyl)-L-phenylalanine methyl ester hydrochloride (0.03 g), (S)-2-phenylpropionic acid (0.014 g), EDC (0.02 g), HOBT (0.021 g) and DIEA (0.034 mL) in DMF (5 mL) was stirred at room temperature for 18 h. DMF was removed and the residue was partitioned between EtOAc and water. The organic layer was evaporated and washed sequentially with 10% citric acid, satd. NaHCO3 and brine. The resulting organic layer was dried (MgSO4), evaporated and the residue was purified by flash column chromatography (silica gel; eluent: CH2Cl2/EtOAc 9:1) to yield N-[(S)-2-phenylpropionyl]-4-(2-methoxyphenyl)-L-phenylalanine methyl ester (0.031 g). ESMS: m/z 417 (MH+).