Photosensitizers for Anticancer Photodynamic Therapy

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Photosensitizers for Anticancer Photodynamic Therapy ( photosensitizers-anticancer-photodynamic-therapy )

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Molecules 2018, 23, 1436 9 of 13 3.2.8. Synthesis of N-Ethyl-N-(5-(3-oxo-3-(2-(5-(2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl) pentanamido)ethylamino)propylamino)-9H-benzo[a]phenoxazin-9-ylidene)ethanaminium Chloride (PS3, C35H44ClN7O4S) To a cold solution of 4 (50 mg, 0.2 mmol, 1 equiv) in EtOH (5 mL) was added 7 (60 mg, 1.2 mmol, 6 equiv) and 5 drops of concentrated HCl. The mixture was refluxed for 4 h. The solution was evaporated and purified by silica gel flash chromatography using CH2Cl2/MeOH (10:1) as eluent to give PS3 as a blue solid (53 mg, 0.12 mmol, 62% yield). 1H-NMR (CD3OD): δ 8.89–8.83 (m, 1H), 8.37 (d, J = 7.5 Hz, 1H), 7.89–7.79 (m, 2H), 7.75–7.55 (m, 2H), 7.29 (d, J = 9.0 Hz, 1H), 7.01 (s, 1H), 6.91 (s, 1H), 4.46 (s, 1H), 4.28 (s, 1H), 4.01 (s, 1H), 3.72–3.71 (m, 4H), 3.56 (s, 1H), 3.15(s, 1H), 2.89–2.74 (m, 2H), 2.66 (s, 1H), 2.15 (s, 1H), 1.67–1.51 (m, 4H), 1.35 (t, J = 7.0 Hz, 1H), 1.17–1.14 (m, 2H). 13C-NMR (CD3OD): δ 176.4, 173.2, 159.1, 155.8, 153.2, 149.8, 134.7, 134.3, 132.9, 132.6, 132.1, 130.9, 125.5, 124.7, 124.0, 121.7, 117.0, 97.0, 94.5, 63.3, 61.6, 56.9, 47.1, 42.0, 41.0, 40.4, 39.9, 36.7, 35.5, 29.7, 29.4, 26.7, 13.0. ESI-MS m/z [M]+ 658.2. HR-ESIMS: [M]+ calcd for C35H44N7O4S+ 658.3170, found 658.3171. 3.2.9. Synthesis of (3S,10R,13S,17S)-17-Acetyl-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17- tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 2-(3-(naphthalen-1-ylamino)propanamido) ethylcarbamate (9, C37H49N3O4) To a solution of (3S,10R,13S,17S)-17-acetyl-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17- tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl 2-(tert-butoxycarbonylamino)ethylcarbamate (8, 300 mg, 0.6 mmol, 1 equiv) in CH2Cl2 (10 mL) was added trifluoroacetic acid (300 μL, 3 mmol, 5 equiv) under 0 ◦C. The mixture was stirred overnight, and then concentrated to give a residue, which was used in the next step without further purification. The above residue was dissolved in CH2Cl2, (10 mL) and then compound 2 (128 mg, 0.6 mmol, 1 equiv), HATU (248 mg, 0.7 mmol, 1.1 equiv) and iPrNEt2 (0.2 mL, 1 mmol, 2 equiv) were added. The mixture was stirred overnight, and then concentrated. The residue was purified by silica gel chromatography with petroleum ether/acetone (1:1) as eluent to give compound 9 as a white solid (205 mg, 0.34 mmol, 57%). 1H-NMR (CDCl3): δ 7.87 (d, J = 7.5 Hz, 1H), 7.78 (m, 2H), 7.46–7.42 (m, 2H), 7.34 (dd, J = 7.9, 7.8 Hz, 1H), 7.25 (d, J = 8.2 Hz, 1H), 6.62 (d, J = 7.5 Hz, 1H), 5.34 (s, 1H), 5.15 (s, 1H), 4.95 (s, 1H), 3.62–3.60 (m, 2H), 3.36 (d, J = 5.4 Hz, 1H), 2.62 (dd, J = 6.1, 6.1 Hz, 1H), 2.53 (dd, J = 9.1, 8.8 Hz, 1H), 2.20–2.14 (m, 3H), 2.12 (s, 3H), 2.05–1.96 (m, 2H), 1.83–1.82 (m, 2H), 1.68–1.43 (m, 9H), 1.25–1.21 (m, 1H), 1.15–1.09 (m, 1H), 0.98 (s, 3H), 0.62 (s, 3H). 13C-NMR (CDCl3): δ 209.8, 172.7, 157.3, 143.6, 139.8, 134.5, 128.7, 126.6, 126.0, 125.0, 123.9, 122.4, 120.3, 117.9, 104.6, 74.8, 63.8, 57.0, 50.0, 44.1, 40.9, 40.7, 40.5, 38.9, 38.6, 37.1, 36.7, 35.4, 31.9, 31.9, 31.7, 28.2, 24.6, 23.0, 21.1, 19.4, 13.4. ESI-MS m/z: [M + H]+ calcd for C37H50N3O4+ 600.4, found 600.1. 3.2.10. Synthesis of N-(5-(3-(2-(((3S,10R,13S,17S)-17-Acetyl-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14, 15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy)carbonylamino)ethylamino)-3- oxopropylamino)-9H-benzo[a]phenoxazin-9-ylidene)-N-ethylethanaminium Chloride (PS4, C47H60ClN5O5) To a cold (ice bath) solution of compound 4 (30 mg, 0.13 mmol, 1.6 equiv) in EtOH (5 mL) was added compound 9 (50 mg, 0.08 mmol, 1 equiv) and 5 drops of concentrated HCl. The mixture was refluxed for 4 h. The solution was evaporated and purified by silica gel flash chromatography using CH2Cl2/MeOH (10:1) as eluent to give compound PS4 as a blue solid (45 mg, 0.06 mmol, 69% yield). 1H-NMR (CD3OD): δ 8.82 (d, J = 11 Hz, 1H), 8.31 (dd, J = 8.3, 8.4 Hz, 1H), 7.88 (dd, J = 7.4, 7.6 Hz, 1H), 7.82 (d, J = 9.2 Hz, 1H), 7.79 (dd, J = 7.3, 7.6 Hz, 1H), 7.28 (d, J = 8.7 Hz, 1H), 6.99 (s, 1H), 6.89 (s, 1H), 5.02 (s, 1H), 4.23 (m, 1H), 3.99–3.97 (m, 2H), 3.72–3.69 (m, 4H), 2.79–2.77 (m, 2H), 2.55 (dd, J = 6.7, 7.0 Hz, 1H), 2.15–2.08 (m, 5H), 1.98 (d, J = 8.2 Hz, 1H), 1.73–1.60 (m, 6H), 1.83–1.82 (m, 2H), 1.38 (d, J = 6.7 Hz, 1H), 1.35 (t, J = 7.2 Hz, 1H), 0.82 (s, 3H), 0.52 (s, 3H). 13C-NMR (CD3OD): δ 212.1, 173.4, 159.0, 158.9, 155.7, 153.0, 149.7, 141.1, 141.1, 134.2, 132.9, 132.6, 130.9, 125.6, 125.5, 124.1, 124.0, 123.0, 116.8, 97.1, 94.7, 75.3, 64.6, 57.9, 51.2, 47.1, 44.9, 41.1, 39.7, 38.0, 37.5, 36.1, 35.6, 35.5, 33.0, 32.9, 32.6, 31.7, 29.1, 25.4, 23.7, 22.0, 19.6, 13.5, 13.0. ESI-MS m/z: [M]+ 774.4. HR-ESIMS: [M]+ calcd for C47H60N5O5+ 774.4589, found 774.4595.

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