, 33 (d, J = 9.2 Hz, 73 mg). 1 H NMR (300 MHz, CDCl3) ? 12 1H), 8.20 (d, J = 9.4 Hz, 1H) 3H), 7.65 (s, 1H), 7.61 (d, J = 7.7 Hz, 1H), 7.54 (dd, J = 7.5, 1.5 Hz, 1H), 7.44 ? 7.35 (m, 1H), 7.33 (s, 1H) 1H), 1.55 (s, 9H), 1.26 (d, J = 6.5 Hz, 7H), 1.20 (d, J = 6.7 Hz, 7H) HRMS (ES + ): m/z calcd for C98H92N17O16 [M+H] + : 1762.6830 found 1762, pp.08889582428107-7, 1994.
, 13 C NMR (75 MHz, CDCl3) ? 163, 3H), 3.94 (d, J = 6.5 Hz, 3H), 3.85 (s, 6H), 3.82 (s, 6H) HRMS (ES + ): m/z calcd for C93H84N17O14 [M+H] + : 1662.6305 found 1662, pp.14-21
, 13, C NMR (75 MHz, CDCl3) ? 163, pp.40-621, 2011.
, 11 (s, 9H) 13 C NMR (75 MHz, CDCl3) ? 163, 8H), 2.36 (dq, J = 13.2, 6.5 Hz, 3H), 2.06 (dt, J = 13.4, 6.7 Hz, 1H), 1.29 ? 1.07 (m, 20H), 1.01 (d, J = 6.7 Hz HRMS (ES + ): m/z calcd for C66H75N12O10Si [M+H] + : 1223.5420 found 1223, pp.4-44
, 312 mmol) was added and the reaction was allowed to stir at room temperature for 3 h. The solvent and excess reagent were removed under vacuum and the residue was dried under vacuum for at least 1 h to yield acid chloride BocHN-Q m -COCl (107) as a white solid To a solution of amine H2N-Q3PN-NHTeoc (106, 0.13 mmol, 160 mg) and distilled DIPEA (0.26 mmol, 0.05 mL) in dry CHCl3 (1 mL) was added dropwise at 0 °C a solution of the freshly prepared acid chloride 107 in dry CHCl3 (1 mL) The reaction was allowed to proceed at room temperature overnight. The solvents were removed under reduced pressure and the residue was purified by precipitation from minimum amount of MeOH to obtain hexamer 108 as a yellow solid, CO2H (0.156 mmol, 58 mg) was suspended in anhydrous CHCl3 (3 mL 173 mg). 1 H NMR (300 MHz, CDCl3) ? 12.20 (s, 1H), 11.69 (s, 1H) 3H), 8.39 (d, J = 9.0 Hz, 1H), pp.2-72
, To a solution of hexamer BocHN-Q m Q3PN-NHTeoc (108, 0.108 mmol, 170 mg) in dry THF (1 mL) under nitrogen was added a solution 1 M of tetrabutylammonium fluoride in THF
, Hexamer amine BocHN-Q m Q3PN-NH2 (109, 0.081 mmol, 120 mg) and acid HO2C-NPyrPyzPyr-CO2TMSE
, 05 mmol, 100 mg) in dry THF (0.5 mL) under nitrogen was added a solution 1 M of tetrabutylammonium fluoride in THF (0.5 mmol, 0.5 mL) The resulting mixture was stirred at room temperature for 16 hours. Volatiles were removed under reduced pressure to give a solid which was dissolved in EtOAc and washed with a 5 % aqueous citric acid solution, distilled water (3 times), and then with brine, The organic layer was dried over MgSO4, filtered and the solvent was removed under reduced pressure to yield the product which was used without any further purification
, 13 C NMR (75 MHz, CDCl3) ? 170, HRMS (ES + ): m/z calcd for C199H190N36O27S [M+2H] 2+ : 1773.7083 found 1773, p.0266554841077285
, mL) Oxalyl chloride (0.165 mmol, 0.015 mL) was added and the reaction was allowed to stir at room temperature for 3 h. The solvent and excess reagent were removed under vacuum and the residue was dried under vacuum for at least 1 h to yield acid chloride FmocHN-Q m -COCl (117) as a yellow solid To a solution of amine H2N-Q3PNN ? -NHBoc (116, 0.032 mmol, 50 mg) and distilled DIPEA (0.064 mmol, 0.005 mL) in dry CHCl3 (0.5 mL) was added dropwise at 0 °C a solution of the freshly prepared acid chloride 117 in dry CHCl3 (1 mL) The reaction was allowed to proceed at room temperature overnight. The solvents were removed under reduced pressure and the residue was purified by chromatography (SiO2) eluting with EtOAc:dichloromethane:cyclohexane obtain heptamer 118 as an orange solid (81 %, 53 mg), CO2H (0.041 mmol, 20 mg) was suspended in anhydrous CHCl3 H NMR (300 MHz, CDCl3) ? 12.25 (s, 1H), 11.76 (s, 1H), 11.46 (s, 1H), 10.87 (s, 1H), 9.77 (s, 1H), 9.70 (s, 1H) 1H), pp.78765423-78765431
, Trifluoroacetic acid Volatiles were removed under reduced pressure to give a solid which was dissolved in dichloromethane and washed with a saturated aqueous solution of NaHCO3, distilled water and then with brine. The organic layer was dried over MgSO4, filtered and the solvent was removed under reduced pressure, the residue was purified by precipitation from minimum amount of MeOH to obtain heptamer 119 as an orange solid (99 %, 47 mg) 1 H NMR (300 MHz, CDCl3) ? 1234 (s, 1H), 11.79 (s, 1H), 11.75 (s, 1H)94 (s, 1H), 50 mg) in 1 mL of chloroform under nitrogen at room temperature. The resulting mixture was stirred at room temperature for 4 hours 1H), 9.77 (s, 1H), 9.74 (s, 1H) 4H), 8.65 (d, J = 7.4 Hz, 1H), 8.24 (d, J = 7.2 Hz, 1H), 8.18 ? 8.11 (m, 3H), 7.98 (d, J = 8.3 Hz, 1H), 7.88 ? 7.61 (m, 9H), 7.55 (s, 1H) 1H), 1.37 ? 1.18 (m, 24H), 0.84 (d, J = 6.6 Hz, 3H), 0.60 (d, J = 6.7 Hz, 3H). 13 C NMR (75 MHz, CDCl3) ? 163.91, 163.86, 163.74 HRMS (ES + ): m/z calcd for C113H107N18O15 [M+H] +, pp.74-82, 1955.
, Amine FmocHN-Q m Q3PNN ? -NH2 (119, 0.024 mmol, 46 mg) and diacid HO2C-PyrPyzPyr-CO2H (28, 0.012 mmol, 3.9 mg) were dissolved in dry chloroform (0.5 mL) DIPEA (0.096 mmol, 0.02 mL) and PyBOP (0.096 mmol, 50 mg) were added at room temperature and the reaction mixture was heated at 45 °C for 18 hours. The solvent was removed under reduced pressure and the residue was, p.29
, 13, C NMR (75 MHz, CDCl3) ? 165.55 HRMS (ES + ): m/z calcd for C242H220N40O32 [M+2H] 2+ : 2098.8331 found 2098
, 96 (s, 12H), 3, 6H), 3.22 (t, J = 5.7 Hz, 2H), 2.97 (dd, J = 17.4, 6.4 Hz, 2H), 2.64 (d, J = 7.4 Hz, 4H) HRMS (ES + ): m/z calcd for C222H216N40O32 [M+2H] 2+, pp.96797573-96797579, 1976.
, 13 C NMR (75 MHz, CDCl3) ? 163, HRMS (ES + ): m/z calcd for 2123M+2H] 2+ : C232H242N42O36Si2 found 2123, pp.4-4