ࡱ> 1307 QbjbjUU ".7|7|l (******$ NNuN`((   p7  0  - - 3,5-di-tert-butylbenzyl alcohol: 3,5-di-tert-butylbenzoic acid (20 g, 85 mmol) was dissolved in 30 mL of dry THF. 1M BH3 (100 mL, 100 mmol) was added via syringe under Ar and the solution was refluxed for 48 h. After the starting material was consumed (as determined by TLC), the solvent was removed in vacuo, and the crude material was dissolved in 30 mL of MeOH. 5.0 mL of 5% HCl was added, and the solution was refluxed for 30 min. After removing the solvents in vacuo, and the crude material was extracted with Et2O/H2O (3 x 100 mL). The organic layers were combined and dried with MgSO4. The crude material was separated on silica using CH2Cl2 as the eluent. 3,5 di-tert-butylbenzyl alcohol (18 g, 82 mmol) was recovered in 97% yield as a white solid: mp 49.5-50.2 C; 1H NMR (CDCl3) d 7.37 (1H, s), 7.22 (2H, s), 4.67 (2H, s), 1.59 (1H, br s), 1.33 (18H, s); 13C NMR (CDCl3) d 150.7, 139.9, 121.3, 121.1, 65.4, 34.6, 31.3. MS m/z [M+Na]+; Anal. Calcd for C15H24ONa: 243.1699. Found: 243.1725. 3,5-di-tert-butylbenzaldehyde: In a dry 250 mL round bottom flask was dissolved 10 mL of DMSO (15 g, 180 mmol) in 75 mL of dry CH2Cl2. The solution was cooled to 78 oC (CO2, acetone) under Ar, 9.0 mL of oxalyl chloride (12 g, 91 mmol) was added via syringe over 10 min, and the reaction was stirred for 20 min. In a separate flask 3,5 di-tbutylbenzyl alcohol (10 g, 46 mmol) was dissolved in 25 mL of dry CH2Cl2, which was added via syringe over 15 min to the activated DMSO. After the reaction was stirred for 45 min, 10 mL of Et3N was added, and the reaction was allowed to warm to room temperature. The crude material was extracted with H2O/CH2Cl2, organic layers were combined, and then dried with MgSO4. After filtering off the drying agent and removing the solvent under reduced pressure, 3,5di-tert-butylbenzaldhyde was obtained in a quantitative yield as a white solid: mp 77-78.5 C; 1H NMR (CDCl3) d 7.73 (1H, s), 7.72 (2H, s), 10.0 (1H, s) 1.34 (18H, s); 13C NMR (CDCl3) d 193.0, 151.8, 136.2, 128.8, 124.1, 34.0, 31.3. MS m/z [M+Na]+; Anal. Calcd for C15H22ONa: 241.1568. Found: 241.1561. N-(2-amino-ethyl)-3,5-di-tert-butylbenzylamine: In a dry 50 mL round bottom flask was added 3,5-di-tert-butyl benzoic acid (2.0 g, 8.5 mmol), carbonyldiimidazole (1.4 g, 10 mmol), and 30 mL of anhydrous CH3CN. The reaction was stirred for 20 min under Ar at room temperature. In a separate dry 50 mL round bottom flask, fitted with an addition funnel, was placed 6 mL of ethylenediamine. The activated 3,5-di-tert-butylbenzoic acid was transferred to the addition funnel and added dropwise to the ethylenediamine over 1 h with rapid stirring. After 3 h, the reaction was extracted with 5% HCl / CHCl3 (3 X 100 mL), and the organic layers were collected, dried over MgSO4, and solvent was removed in vacuo. The crude material was separated on silica using CHCl3 containing 5% MeOH. To obtain the free amine, the product was extracted with 2N NaOH / CHCl3 (3 X 100 mL), and the organic layers were combined and dried with MgSO4, affording the desired product (2.3 g, 8.2 mmol) in 97% yield as a white solid: mp 191-192 C; 1H NMR (CDCl3) d 7.60 (2H, s), 7.57 (1H, s), 6.61 (1H, s), 3.52 (2H, dd, J = 6 Hz) 2.96 (2H, t, J = 6 Hz), 1.34 (18H, s); 13C NMR (CDCl3) d 168.8, 151.0, 134.1, 125.4, 121.0, 42.5, 41.3, 34.8, 31.3. FT/IRC/MS m/z [M+H]+; Anal. Calcd for C17H29N2O: 277.2274. Found: 277.2275. N-3,5-di-tert-butylbenzyl-5-amino-valeric acid: In a dry 50 mL round bottom flask was placed valeric acid (1.6 g, 9.0 mmol), Et4NOH (1.9 g, 9.0 mmol), and 20 mL of a 50/50 MeOH/CHCl3 solution. The resulting cloudy mixture was dried with Na2SO4 for 20 min. 3,5-di-tert-butylbenzaldehyde7 (1.0 g, 4.5 mmol) was added to the solution and stirred under Ar for 1 h. After filtering, NaBH4 (340 mg, 9.0 mmol) was added under rapid stirring. The reaction was left for 1 h, dried under high vacuum exhaustively, and the crude material was extracted with 5% HCl/CHCl3. The organic layers were combined and dried over MgSO4. Separation of the crude material was accomplished via HPLC using H2O / 1 % TFA as the eluent, affording N-3,5 di-tert-butylbenzyl-5-amino valeric acid TFA salt in a 45% yield as a white solid: mp 159-161 C; 1H NMR (CDCl3) d 10.9 (1H, s), 8.91 (3H, s), 7.41 (1H, s), 7.33 (2H, s), 4.11 (2H, br s), 2.89 (2H, t, J = 6.7 Hz), 2.31 (2H, t, J = 6.7 Hz), 1.85 (2H, m), 1.61 (2H, m), 1.29 (18H, s); 13C NMR (CDCl3) d 177.3, 151.9, 129.1, 124.3, 123.4, 51.7, 46.1, 34.8, 33.1, 31.3, 25.2, 21.6. ESI MS m/z [M]+; Anal. Calcd for C20H34NO2: 320.258. Found: 320.2540.  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