Reaction SMILES: Cl.[CH:2]1([C@H:5]([NH2:10])[C:6]([F:9])([F:8])[F:7])[CH2:4][CH2:3]1.C(N(CC)C(C)C)(C)C.C[Al](C)C.[C:24]([CH2:26][C:27]1([N:41]2[CH:45]=[C:44]([C:46]3[C:47]4[CH:54]=[CH:53][N:52](COCC[Si](C)(C)C)[C:48]=4[N:49]=[CH:50][N:51]=3)[CH:43]=[N:42]2)[CH2:30][N:29]([C:31]2[CH:40]=[CH:39][C:34]([C:35](OC)=[O:36])=[CH:33][CH:32]=2)[CH2:28]1)#[N:25]>ClCCCl.C1(C)C=CC=CC=1.ClCCl>[C:24]([CH2:26][C:27]1([N:41]2[CH:45]=[C:44]([C:46]3[C:47]4[CH:54]=[CH:53][NH:52][C:48]=4[N:49]=[CH:50][N:51]=3)[CH:43]=[N:42]2)[CH2:30][N:29]([C:31]2[CH:32]=[CH:33][C:34]([C:35]([NH:10][C@@H:5]([CH:2]3[CH2:4][CH2:3]3)[C:6]([F:9])([F:8])[F:7])=[O:36])=[CH:39][CH:40]=2)[CH2:28]1)#[N:25]
Reactant: N[C@@H](C1CC1)C(F)(F)F
Reactant: COC(=O)c1ccc(N2CC(CC#N)(n3cc(-c4ncnc5c4ccn5COCC[Si](C)(C)C)cn3)C2)cc1
Agent: C[Al](C)C
Agent: Cl
Solvent: Cc1ccccc1
Solvent: ClCCCl
Solvent: ClCCl
Product: N#CCC1(n2cc(-c3ncnc4[nH]ccc34)cn2)CN(c2ccc(C(=O)N[C@@H](C3CC3)C(F)(F)F)cc2)C1
Temperature: 25 °C
Reaction time: 0.33 h
Yield: 94 %

Procedure:
To an oven dried vial containing (15)-1-cyclopropyl-2,2,2-trifluoroethanamine HCl salt (130 mg, 0.74 mmol) (ASIBA Pharmatech, Cat. #: 70092-HCl) and equipped with a magnetic stirring bar was placed anhydrous 1,2-dichloroethane (0.5 mL) followed by N,N-diisopropylethylamine (140 μL, 0.83 mmol). The reaction vial was purged with N2 (g) and sealed prior to the addition of 2.0 M trimethylaluminum in toluene (180 μL, 0.37 mmol). After stirring at room temperature for 20 min., a solution of methyl 4-{3-(cyanomethyl)-3-[4-(7-{[2-(trimethylsilyl)ethoxy]methyl}-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]azetidin-1-yl}benzoate (100. mg, 0.184 mmol) (Example 19, Step 1) in 1,2-dichloroethane (1.0 mL) was added and the reaction mixture was heated at 65° C. and stirred for 16 h. LCMS data indicated that the reaction was ˜50% complete. A second aliquot of a pre-stirred solution of (15)-1-cyclopropyl-2,2,2-trifluoroethanamine HCl salt (130 mg), N,N-diisopropylethylamine (140 μL), and 2.0 M trimethylaluminum in toluene (180 μL) in 1,2-dichloroethane (0.5 mL) was added and stirring was continued for 4 h. LC/MS data indicated that the reaction was complete. Upon cooling to room temperature, the reaction mixture was diluted with dichloromethane (4 mL) and DOWEX 50WX8-400 ion-exchange resin was carefully added to the reaction mixture. After stirring at room temperature for 30 min, the inorganics were filtered off and thoroughly washed with dichloromethane. The crude reaction mixture was purified by flash chromatography on a silica gel column with methanol in dichloromethane (0-10%) to afford the desired product (90 mg, 75% yield). The pure product was dissolved in dichloromethane (2 mL) and trifluoroacetic acid (2 mL) and was stirred at room temperature for 1 h. The volatiles were removed under reduced pressure and the residue was azeotropically washed with acetonitrile (3×3 mL). The resulting residue was dissolved in methanol (3 mL), and NH4OH aqueous solution (200 μL) and ethylenediamine (50 μL) were added and the reaction mixture was stirred at room temperature for 1 h. The crude reaction mixture was subjected to RP-HPLC (pH=2) to afford the desired product as the corresponding trifluoroacetic acid salt as a white solid. LCMS (M+H)+: m/z=521.2. 1H NMR (500 MHz, DMSO-d6): δ 12.48 (s, 1H), 9.03 (s, 1H), 8.80 (s, 1H), 8.66 (d, J=8.9 Hz, 1H), 8.53 (s, 1H), 7.84 (d, J=8.7 Hz, 2H), 7.73 (s, 1H), 7.18 (s, 1H), 6.62 (d, J=8.7 Hz, 2H), 4.58 (d, J=8.7 Hz, 2H), 4.33 (d, J=8.7 Hz, 2H), 4.08 (dt, J=17.3, 8.6 Hz, 1H), 3.76 (s, 2H), 1.30-1.19 (m, 1H), 0.68 (dt, J=12.4, 5.6 Hz, 1H), 0.51 (q, J=7.8, 6.8 Hz, 2H), 0.29-0.23 (m, 1H).