Propargyl-PEG7-alcohol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diisopropyl azodicarboxylate (730 μL, 3.43 mmol) was added dropwise into the ice cooled solution of 3,6,9,12,15,18-hexaoxahenicos-20-yn-1-ol 1 (1000 mg, 3.12 mmol), triphenylphosphine (900 mg, 3.43 mmol) and maleimide (456 mg, 4.70 mmol) in anhydrous THF (20 mL) under nitrogen atmosphere (FIG. 3). The resulting brown solution was allowed to war to room temperature and stirred for 1 hour at room temperature. The solvent was evaporated at the reduced pressure and the crude product was purified on a SiO2 column using hexanes/ethylacetate gradient 0-100% to yield 650 mg of yellow oil which was subsequently purified on semipreparative HPLC (System E) to provide 2 free of triphenylphosphine oxide as colorless oil 310 mg (25%). 1H NMR (400 MHz, CDCl3): δ 2.43 (t, J=2.36 Hz, 1H), 3.60-3.72 (m, 24H), 4.20 (d, J=2.37 Hz, 2H), 6.70 (s, 2H); 13C NMR (100.6 MHz, CDCl3): δ 37.2, 58.4, 67.8, 69.1, 70.1, 70.4-70.6, 74.5, 79.7, 134.1, 170.6; MS ESI (m/z): [M+H]+, calcd. for C19H30NO8, 400.19. found 400.0 was allowed to war to room temperature The solvent was evaporated at the reduced pressure the crude product was purified on a SiO2 column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diisopropyl azodicarboxylate (730 μL, 3.43 mmol) was added dropwise into the ice cooled solution of 3,6,9,12,15,18-hexaoxahenicos-20-yn-1-ol 1 (1000 mg, 3.12 mmol), triphenylphosphine (900 mg, 3.43 mmol) and maleimide (456 mg, 4.70 mmol) in anhydrous THF (20 mL) under nitrogen atmosphere (FIG. 3). The resulting brown solution was allowed to war to room temperature and stirred for 1 hour at room temperature. The solvent was evaporated at the reduced pressure and the crude product was purified on a SiO2 column using hexanes/ethylacetate gradient 0-100% to yield 650 mg of yellow oil which was subsequently purified on semipreparative HPLC (System E) to provide 2 free of triphenylphosphine oxide as colorless oil 310 mg (25%). 1H NMR (400 MHz, CDCl3): δ 2.43 (t, J=2.36 Hz, 1H), 3.60-3.72 (m, 24H), 4.20 (d, J=2.37 Hz, 2H), 6.70 (s, 2H); 13C NMR (100.6 MHz, CDCl3): δ 37.2, 58.4, 67.8, 69.1, 70.1, 70.4-70.6, 74.5, 79.7, 134.1, 170.6; MS ESI (m/z): [M+H]+, calcd. for C19H30NO8, 400.19. found 400.0 was allowed to war to room temperature The solvent was evaporated at the reduced pressure the crude product was purified on a SiO2 column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride, 60% dispersion in mineral oil, (0.86 g, 21.4 mmol) was added in portions to the solution of hexaethylene glycol (5.5 g, 19.4 mmol) in anhydrous THF (40 mL) at 0° C. (FIG. 3). The reaction mixture was stirred at 0° C. for 15 minutes then propargyl bromide, 80% in toulene, (2.4 mL, 21.4 mmol) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 3 hours. The formed sodium bromide was removed by filtration and the solvent was evaporated. The crude product was purified on SiO2 column using methanol/dichloromethane gradient 0-100% to yield 3.4 g (54%) of 1 as a colorless oil. 1H NMR (500 MHz, CDCl3): δ 2.45 (t, J=2.4 Hz, 1H), 2.74 (bs, 1H), 3.61-3.71 (m, 24H), 4.21 (d, J=2.4 Hz, 2H); 13C NMR (100.6 MHz, CDCl3): δ 58.4, 61.7, 69.1, 70.3-70.6, 72.5, 74.5, 79.7; MS ESI (m/z): [M+H]− calcd. for C15H29O7, 321.38. found 321.4. to warm to room temperature stirred for 3 hours The formed sodium bromide was removed by filtration the solvent was evaporated The crude product was purified on SiO2 column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diisopropyl azodicarboxylate (730 μL, 3.43 mmol) was added dropwise into the ice cooled solution of 3,6,9,12,15,18-hexaoxahenicos-20-yn-1-ol 1 (1000 mg, 3.12 mmol), triphenylphosphine (900 mg, 3.43 mmol) and maleimide (456 mg, 4.70 mmol) in anhydrous THF (20 mL) under nitrogen atmosphere (FIG. 3). The resulting brown solution was allowed to war to room temperature and stirred for 1 hour at room temperature. The solvent was evaporated at the reduced pressure and the crude product was purified on a SiO2 column using hexanes/ethylacetate gradient 0-100% to yield 650 mg of yellow oil which was subsequently purified on semipreparative HPLC (System E) to provide 2 free of triphenylphosphine oxide as colorless oil 310 mg (25%). 1H NMR (400 MHz, CDCl3): δ 2.43 (t, J=2.36 Hz, 1H), 3.60-3.72 (m, 24H), 4.20 (d, J=2.37 Hz, 2H), 6.70 (s, 2H); 13C NMR (100.6 MHz, CDCl3): δ 37.2, 58.4, 67.8, 69.1, 70.1, 70.4-70.6, 74.5, 79.7, 134.1, 170.6; MS ESI (m/z): [M+H]+, calcd. for C19H30NO8, 400.19; found 400.0 was allowed to war to room temperature The solvent was evaporated at the reduced pressure the crude product was purified on a SiO2 column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride, 60% dispersion in mineral oil, (0.86 g, 21.4 mmol) was added in portions to the solution of hexaethylene glycol (5.5 g, 19.4 mmol) in anhydrous THF (40 mL) at 0° C. (FIG. 3). The reaction mixture was stirred at 0° C. for 15 minutes then propargyl bromide, 80% in toluene, (2.4 mL, 21.4 mmol) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 3 hours. The formed sodium bromide was removed by filtration and the solvent was evaporated. The crude product was purified on SiO2 column using methanol/dichloromethane gradient 0-100% to yield 3.4 g (54%) of 1 as a colorless oil. 1H NMR (500 MHz, CDCl3): δ 2.45 (t, J=2.4 Hz, 1H), 2.74 (bs, 1H), 3.61-3.71 (m, 24H), 4.21 (d, J=2.4 Hz, 2H); 13C NMR (100.6 MHz, CDCl3): δ 58.4, 61.7, 69.1, 70.3-70.6, 72.5, 74.5, 79.7; MS ESI (m/z): [M+H]+ calcd. for C15H29O7, 321.38; found 321.4. to warm to room temperature stirred for 3 hours The formed sodium bromide was removed by filtration the solvent was evaporated The crude product was purified on SiO2 column

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diisopropyl azodicarboxylate (730 μL, 3.43 mmol) was added dropwise into the ice cooled solution of 3,6,9,12,15,18-hexaoxahenicos-20-yn-1-ol 1 (1000 mg, 3.12 mmol), triphenylphosphine (900 mg, 3.43 mmol) and maleimide (456 mg, 4.70 mmol) in anhydrous THF (20 mL) under nitrogen atmosphere (FIG. 3). The resulting brown solution was allowed to war to room temperature and stirred for 1 hour at room temperature. The solvent was evaporated at the reduced pressure and the crude product was purified on a SiO2 column using hexanes/ethylacetate gradient 0-100% to yield 650 mg of yellow oil which was subsequently purified on semipreparative HPLC (System E) to provide 2 free of triphenylphosphine oxide as colorless oil 310 mg (25%). 1H NMR (400 MHz, CDCl3): δ 2.43 (t, J=2.36 Hz, 1H), 3.60-3.72 (m, 24H), 4.20 (d, J=2.37 Hz, 2H), 6.70 (s, 2H); 13C NMR (100.6 MHz, CDCl3): δ 37.2, 58.4, 67.8, 69.1, 70.1, 70.4-70.6, 74.5, 79.7, 134.1, 170.6; MS ESI (m/z): [M+H]+, calcd. for C19H30NO8, 400.19. found 400.0 was allowed to war to room temperature The solvent was evaporated at the reduced pressure the crude product was purified on a SiO2 column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride, 60% dispersion in mineral oil, (0.86 g, 21.4 mmol) was added in portions to the solution of hexaethylene glycol (5.5 g, 19.4 mmol) in anhydrous THF (40 mL) at 0° C. (FIG. 3). The reaction mixture was stirred at 0° C. for 15 minutes then propargyl bromide, 80% in toulene, (2.4 mL, 21.4 mmol) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 3 hours. The formed sodium bromide was removed by filtration and the solvent was evaporated. The crude product was purified on SiO2 column using methanol/dichloromethane gradient 0-100% to yield 3.4 g (54%) of 1 as a colorless oil. 1H NMR (500 MHz, CDCl3): δ 2.45 (t, J=2.4 Hz, 1H), 2.74 (bs, 1H), 3.61-3.71 (m, 24H), 4.21 (d, J=2.4 Hz, 2H); 13C NMR (100.6 MHz, CDCl3): δ 58.4, 61.7, 69.1, 70.3-70.6, 72.5, 74.5, 79.7; MS ESI (m/z): [M+H]− calcd. for C15H29O7, 321.38. found 321.4. to warm to room temperature stirred for 3 hours The formed sodium bromide was removed by filtration the solvent was evaporated The crude product was purified on SiO2 column