Compound 2
4-[4-({2,19,21,38,53,54-hexaethyl-6,15,25,34,41,50-hexaoxo-30,45-bis[(4-oxo-1,1-bis{3-oxo-3-[3-oxycarbonyl-1,1-bis(2-oxycarbonylethyl)propylamino]propyl}-4-[3-oxycarbonyl-1,1-bis(2-oxycarbonylethyl)propylamino]butylamino)carbonyl]-5,7,14,16,24,26,33,35,40,42,49,51-didecaazaheptacyclo[18.18.14.13,37.118,22.08,13.027,32.043,48]tetrapentaconta-1,3(53),8,10,12,18(54),19,21,27,29,31,37,43,45,47-pentadecaen-10-yl}carbonylamino)-7-oxo-4-{3-oxo-3-[3-oxycarbonyl-1,1-bis(2-oxycarbonylethyl)propylamino]propyl}-7-[3-oxycarbonyl-1,1-bis(2-oxycarbonylethyl)propylamino]heptanoylamino]-4-(2-oxycarbonylethyl)heptanedioate
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- Glucose receptor
Compound data: 1H NMR
Compound data: 13C NMR
Compound data: COSY
Compound data: HSQC
Compound data: HMBC
Compound data: NOESY
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
Under an inert N2 atmosphere, the half-receptor 8 (500 mg, 0.1 mmol), octyl β-D-glucoside 9 (59 mg, 0.2 mmol) and 4-dimethylaminopyridine (37 mg, 0.3 mmol) were dissolved in anhydrous dichloromethane (180 mL). A solution of 7 (33 mg, 0.1 mmol) in anhydrous dichloromethane (20 mL) was added at a rate of 1 mL/hr and the reaction stirred at 34 °C for 2 days. The reaction mixture was cooled to room temperature and the solvent removed under vacuum. The residue was purified by preparative HPLC (Waters CSH C18 5 µm 19 × 250 mm) eluting with acetone/water (70:30 → 96:4 over 30 mins, then 96:4 isocratic over 10 mins, then 100:0 over 5 mins). The solvent was removed under vacuum and the product suspended in water and freeze dried to afford C as a white solid (257 mg, 0.048 mmol, 48%). 1H NMR: (400 MHz, (CD3OD): δ 1.21 (m, 18H C(1)H3), 1.43 (s, 243H, C(23)H3), 1.95 (m, 54H, C(20)H2), 2.13 (m, 18H, C(15)H2), 2.20 (m, 54H, C(19)H2), 2.25 (m, 18H, C(16)H2), 2.72, 2.83 (br m, 6H, C(2)H2), 4.40, 4.49 (br s, 6H, C(5)H2), 7.43 (s, 9H, NH), 7.63 (d, J = 8.7 Hz, 3H, C(10)H), 8.04 (d, J = 8.7 Hz, 3H, C(11)H), 8.06 (s, 3H, C(8)H); 13C NMR: (100 MHz, (CDCl3): δ 15.5, 15.6 (C1), 22.3, 22.5 (C2), 27.1 (C23), 29.1 (C19), 29.3 (C20), 30.8 (C15), 31.0 (C16), 37.5 (C5), 57.3 (C18), 58.1 (C14), 80.2 (C22), 120.3 (C11), 123.5 (C8), 124.1 (C10), 127.6 (C7), 129.4 (C9), 132.0, 132.6 (C3), 135.0 (C12), 143.0, 143.2 (C4), 155.8, 156.6 (C6), 168.2 (C13), 173.0 (C21), 174.1 (C17); HRMS: (ESI+) calculated for C285H462N24O72Na33+ 1816.1084 found [M+3Na]3+: 1816.1093. Protected receptor C (50 mg, 9.3 µmol) was dissolved in dichloromethane (HPLC grade, 2 ml) and cooled to 0 °C. Trifluoroacetic acid (TFA) (0.5 mL) was added dropwise and the reaction warmed to room temperature and stirred for 16 hours. The solvent was then removed under a flow of nitrogen, then the residue was co-evaporated with toluene (3 x 10 mL) to remove residual TFA, suspended in water and freeze dried. The product was then purified by preparative HPLC (Waters CSH C18 5 µm 19 × 250 mm) eluting with 100% Water (buffered with 0.1 % TFA) → 100% methanol over 40 minutes. The solvent was removed under vacuum, the residue co-evaporated with toluene (3 × 10 mL), the product suspended in water and freeze dried. The solid was then suspended in water, neutralised to pH 7.4 with NaOH (aq), filtered and then freeze dried to afford 2 as a white solid (36.9 mg, 8.3 µmol, 89%). 1H NMR: (400 MHz, (D2O): δ 0.93-1.12,1.11-1.25 (br m, 18H, C(1)H3), 1.89-1.98 (m, 54H, C(20)H2), 2.08-2.15 (m, 18H, C(15)H2), 2.13- 2.20 (m, 54H, C(19)H2), 2.27-2.35 (m, 18H, C(16)H2), 2.67-2.85 (br m, 12 jH, C(2)H2), 4.46 (br s, 6H, C(5)H2), 7.63 (d, J = 8.3 Hz, 3H, C(10)H), 7.78 (br s, 3H, C(8)H),7.80-7.85 (br m, 3H, C(11)H); 13C NMR: (100 MHz, (CDCl3): δ 15.4, 15.5 (C1), 22.4, 22.6 (C2), 30.3 (C19), 30.5 (C15), 30.8 (C16), 31.1 (C20), 37.5, 37.7 (C5), 58.2 (C18), 58.6 (C14),122.4 (C11), 124.9 (C8, C10), 128.4 (C7), 130.0 (C9), 132.0, 132.4 (C3), 135.6 (C12), 144.0, 144.2 (C4), 157.0, 157.7 (C6), 169.6 (C13), 175.2 (C17), 182.1 (C21)
