Reaction SMILES: [CH:1]1([C@H:4]([NH2:6])[CH3:5])[CH2:3][CH2:2]1.C[Al](C)C.C1(C)C=CC=CC=1.[C:18]([CH2:20][C:21]1([N:36]2[CH:40]=[C:39]([C:41]3[C:42]4[CH:49]=[CH:48][N:47](COCC[Si](C)(C)C)[C:43]=4[N:44]=[CH:45][N:46]=3)[CH:38]=[N:37]2)[CH2:24][N:23]([C:25]2[CH:34]=[CH:33][C:28]([C:29](OC)=[O:30])=[C:27]([F:35])[CH:26]=2)[CH2:22]1)#[N:19]>ClCCCl>[C:18]([CH2:20][C:21]1([N:36]2[CH:40]=[C:39]([C:41]3[C:42]4[CH:49]=[CH:48][NH:47][C:43]=4[N:44]=[CH:45][N:46]=3)[CH:38]=[N:37]2)[CH2:22][N:23]([C:25]2[CH:34]=[CH:33][C:28]([C:29]([NH:6][C@@H:4]([CH:1]3[CH2:3][CH2:2]3)[CH3:5])=[O:30])=[C:27]([F:35])[CH:26]=2)[CH2:24]1)#[N:19]
Reactant: C[C@@H](N)C1CC1
Reactant: COC(=O)c1ccc(N2CC(CC#N)(n3cc(-c4ncnc5c4ccn5COCC[Si](C)(C)C)cn3)C2)cc1F
Agent: C[Al](C)C
Solvent: Cc1ccccc1
Solvent: ClCCCl
Product: C[C@@H](NC(=O)c1ccc(N2CC(CC#N)(n3cc(-c4ncnc5[nH]ccc45)cn3)C2)cc1F)C1CC1
Temperature: 25 °C
Reaction time: 0.5 h

Procedure:
To a sealed vial that was purged with N2 (g) and contained a solution of (1R)-1-cyclopropylethanamine (150 μL, 1.62 mmol) (Alfa Aesar 1-126902 lot 10151885, CAS 6240-96-9, 98% ee) in 1,2-dichloroethane (2 mL) was added 2.0 M trimethylaluminum in toluene (0.800 mL, 1.60 mmol) via syringe and the resulting solution was stirred at room temperature for 30 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}-2-fluorobenzoate (300. mg, 0.534 mmol) (Example 15, Step 1) in 1,2-dichloroethane (3 mL) was added drop-wise via syringe. The solution was heated to 70° C. and stirred for 16 h. LCMS data indicated that ˜60% of the starting material was converted to the desired product. In an effort to drive the reaction to completion a pre-stirred solution of (1R)-1-cyclopropylethanamine (150 μL) and 2.0 M trimethylaluminum in toluene (800 μL) in 1,2-dichloroethane (2 mL) was added via syringe to the reaction mixture at room temperature. The reaction mixture was then heated to 70° C. and stirred for 16 h. LCMS data indicated that the majority of the starting material was converted to the desired product. Upon cooling to room temperature, the reaction mixture was diluted with dichloromethane (5 mL) and DOWEX 50WX8-400 ion-exchange resin was carefully added and the reaction mixture was stirred for 30 min. The inorganics were filtered off and thoroughly washed with dichloromethane. The filtrate was concentrated under reduced pressure and the residue was purified by flash chromatography on a silica gel column with methanol in dichloromethane (0-5%) to afford the desired product (100 mg). The product was dissolved in dichloromethane (4 mL) and TFA (4 mL) and was stirred at room temperature for 1.5 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 (4 mL) and NH4OH aqueous solution (1 mL) was added and the reaction mixture was stirred at room temperature for 1 h. The crude reaction mixture was concentrated under reduced pressure and subjected to flash chromatography on a silica gel column with methanol in dichloromethane (0-10%) to afford the desired product. The product was dissolved in acetonitrile (15 mL) and cooled to 0° C. prior to the addition of trifluoroacetic acid (0.08 mL). The reaction mixture was allowed to warm to ambient temperature while stirring for 30 min. Water (10 mL) was added and the solution was frozen and subjected to lyophilization to afford the desired product as the corresponding trifluoroacetic acid salt as a white solid. LCMS (M+H)+: m/z=485.5. 1H NMR (500 MHz, CD3OD): δ 9.02 (s, 1H), 8.85 (s, 1H), 8.53 (s, 1H), 7.78 (d, J=3.7 Hz, 1H), 7.67 (t, 8.5 Hz, 1H), 7.26 (d, J=3.7 Hz, 1H), 6.47 (dd, J=8.6, 2.0 Hz, 1H), 6.40 (dd, 13.5, 1.9 Hz, 1H), 4.61 (d, J=8.7 Hz, 2H), 4.44 (d, J=8.7 Hz, 2H), 3.67 (s, 2H), 3.51 (p, J=6.8 Hz, 1H), 1.29 (d, J=6.7 Hz, 3H), 0.98 (ddt, J=13.2, 8.3, 4.2 Hz, 1H), 0.54 (td, J=8.4, 4.5 Hz, 1H), 0.47 (tt, J=8.9, 5.3 Hz, 1H), 0.37 (dq, J=9.8, 5.0 Hz, 1H), 0.26 (dq, J−9.5, 4.9 Hz, 1H).