Introduction of a new synthetic route about 135908-33-7

Statistics shows that Methyl 4-aminobicyclo[2.2.2]octane-1-carboxylate is playing an increasingly important role. we look forward to future research findings about 135908-33-7.

Related Products of 135908-33-7, These common heterocyclic compound, 135908-33-7, name is Methyl 4-aminobicyclo[2.2.2]octane-1-carboxylate, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route.

General procedure: Example 69: 4-(((6-((trans-4-(tert-butyl)cyclohexyl)oxy)quinolin-2-yl)methyl)amino)bicyclo[2.2.2] octane-l-carboxylic acid Step 1: methyl 4-(((6-((trans-4-(tert-butyl cyclohexyl oxy quinolin-2-yl methyl amino bicyclor2.2.21oct ane- 1 -carboxylate 2) NaBH(OAc)3 (3 eq), it, 1 h Y: 30% The solution of 6-((trans-4-(tert-butyl)cyclohexyl)oxy)quinoline-2-carbaldehyde (200 mg, 0.6 mmol) and methyl 4-aminobicyclo[2.2.2]octane-l-carboxylate (142 mg, 0.644 mmol) in Ethanol (2 mL, 30 mmol) was heated to reflux for 2h. The yellow solution was cooled to room temperature and sodium cyanoborohydride (48.6 mg, 0.773 mmol) was added and was heated to reflux for lh. After cooled down to room temperature, citric acid was added and concentrated down. The solid was suspended in water and filtrate, and the collected solid was washed thoroughly with water. HPLC purification of the solid give the product (62.7 mg, 20%). LCMS Rt = 1.67 min, m/z = 479.30 [M+l]. Lithium hydroxide (15.7 mg, 0.655 mmol) was added to a solution of 4-{ [6-(trans-4-tert-Butyl-cyclohexyloxy)-quinolin-2-ylmethyl]-amino}-bicyclo[2.2.2]octa ne-l-carboxylic acid methyl ester (62.7 mg, 0.131 mmol) in tetrahydrofuran (0.8 mL, 10 mmol) and methanol (0.8 mL, 20 mmol). The mixture was stirred at 50 C overnight, the solvent was concentrated. The residue was taken up in DMSO and cone. HCl (200 uL) was added to solubilize. Purification by preparative HPLC gave the product as a white solid (63 mg, 20%). LCMS (100%, RT=1.57 min, m/z=465.30. 1H NMR (400 MHz, METHANOL-d4) delta ppm 0.94 (s, 9 H) 1.06 – 1.60 (m, 5 H), 1.86 – 1.99 (m, 2H), 2.00- 2.10 (m, 12 H), 2.24 – 2.37 (m, 2 H) 4.32 – 4.46 (m, 1 H) 4.49 (s, 2 H) 7.34 (d, J=2.51 Hz, 1 H) 7.42 (dd, J=9.29, 2.76 Hz, 1 H), 7.47 (d, J=8.53 Hz, 1 H) 8.01 (d, J=9.29 Hz, 1 H) 8.28 (d, J=8.28 Hz, 1 H). Step 2: 4-(((6-((trans-4-(tert-butyl)cvclohexyl)oxy)quinolin-2-yl)methyl)amino)bicyclor2.2.21oct ane-l-carboxylic acid Lithium hydroxide (15.7 mg, 0.655 mmol) was added to a solution of 4-{ [6-(trans-4-tert-butyl-cyclohexyloxy)-quinolin-2-ylmethyl]-amino}-bicyclo[2.2.2]octa ne-l-carboxylic acid methyl ester (62.7 mg, 0.131 mmol) in tetrahydrofuran (0.8 mL, 10 mmol) and methanol (0.8 mL, 20 mmol). The mixture was stirred at 50 C overnight, the solvent was concentrated. The residue was taken up in DMSO and cone. HCl (200 uL) was added to solubilize. Purification by preparative HPLC gave the product as a white solid (2.3 mg, 4%). LCMS (100%, RT=1.57 min, m/z=465.30. 1H NMR (400 MHz, METHANOL-d4) delta ppm 0.94 (s, 9 H) 1.06 – 1.60 (m, 5 H), 1.86 – 1.99 (m, 2H), 2.00- 2.10 (m, 12 H), 2.24 – 2.37 (m, 2 H) 4.32 – 4.46 (m, 1 H) 4.49 (s, 2 H) 7.34 (d, J=2.51 Hz, 1 H) 7.42 (dd, J=9.29, 2.76 Hz, 1 H), 7.47 (d, J=8.53 Hz, 1 H) 8.01 (d, J=9.29 Hz, 1 H) 8.28 (d, J=8.28 Hz, 1 H).

Statistics shows that Methyl 4-aminobicyclo[2.2.2]octane-1-carboxylate is playing an increasingly important role. we look forward to future research findings about 135908-33-7.

Reference:
Patent; BIOGEN IDEC MA INC.; GUCKIAN, Kevin; KUMARAVEL, Gnanasambandam; MA, Bin; MI, Sha; PENG, Hairuo; SHAO, Zhaohui; SUN, Lihong; TAVERAS, Arthur; XIN, Zhili; ZHANG, Lei; WO2014/18891; (2014); A1;,
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