Synthesis of glycoporphyrins using trichloroacetimidates as glycosyl donors

Synlett

Volumn , Issue 3, 2010, Pages 395-398

  Aicher, Daniel ^a   Wiehe, Arno ^b,c   Stark, Christian B W ^a  

^a UNIVERSITY OF LEIPZIG   (Germany)

^b FREIE UNIVERSITÄT BERLIN   (Germany)

^c Biolitec AG   (Germany)

Author keywords

Antitumor agents; Glycoconjugates; Glycosylations; Photodynamic therapy; Porphyrins

Indexed keywords

ANTINEOPLASTIC AGENT; GLYCOCONJUGATE; GLYCOPORPHYRIN DERIVATIVE; LEWIS ACID; PORPHYRIN DERIVATIVE; TRICHLOROACETIMIDIC ACID; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CONJUGATION; DRUG STRUCTURE; DRUG SYNTHESIS; GLYCOSYLATION; PHOTODYNAMIC THERAPY; QUANTUM YIELD; REACTION ANALYSIS; RELIABILITY;

EID: 76249119464     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1219355     Document Type: Article

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39. Typical Glycosylation Procedure Zn(II) 5-(3-hydroxyphenyl)-10,15,20- triphenylporphyrin (2a, 100 mg, 0.14 mmol) was dissolved in dry CH2Cl2 (20 mL) under an argon atmosphere. Then 2,3,4,6-tetra-Oacetyl-b-D-gluco-pyranosyl trichlor acetimidate (130 mg, 0.26 mmol, 1.85 equiv) or 2,3,4,6-tetra-O-acetyl- a-Dgalacto- pyranosyl trichloroacetimidate (350 mg, 0.70 mmol, 5.0 equiv) was added in three portions followed by BF3OEt2 (5.0 mL, 0.04 mmol). After stirring for 15 min for glucosylation or 120 min for galactosylation the mixture was transferred to a separatory funnel. The organic layer was washed with H2O (250 mL), and the solvent was evaporated under reduced pressure. The residue was dissolved in THF (20 mL) and HCl (25%, 0.5 mL) were added. After stirring for 10 min H2O (50 mL) and CH2Cl2(75 mL) were added. The organic layer was separated and washed with H2O (250 mL). After drying with Na2SO4 the solvent was evaporated under reduced pressure. Further purification was achieved by flash chromatography using CH2Cl2EtOAc (95:5) as the eluent. The analytically pure roduct was obtained as a violet crystalline solid after recrystallization from CH2Cl2MeOH. 5-[3-(2,3,4,6-Tetraacetyl-b-D-glucosyl)phenyl]-10,15,20- triphenylporphyrin (3a) Yield 123 mg, 89%; mp 205 C. 1H NMR (500 M z, CDCl3): d = 2.70 (m, 2 H, NH), 1.37 (s, 3 H, OAc), 2.02 (s, 3 H, OAc), 2.07 (s, 3 H, OAc), 2.12 (s, 3 H, OAc), 3.83 (ddd, J = 2.4, 5.8, 10.0 Hz, 1 H, H-5ose), 4.08 (dd, J = 2.4, 12.2 Hz, 1 H, H-6Aose), 4.20 (dd, J = 5.8, 12.2 Hz, 1 H, H- 6Bose), 5.20 (dd, J = 9.1, 10.0 Hz, 1 H, H-4ose), 5.32 (dd, J = 9.1, 9.1 Hz, 1 H, H-3ose), 5.35 (d, J = 7.8 Hz, 1 H, H- 1ose), 5.40 (dd, J = 7.8, 9.1 Hz, 1 H, H-2ose), 7.427.45(m, 1 H, Ar), 7.667.69 (m, 1 H, Ar), 7.747.81 (m, 9 H, Ph), 7.887.89 (m, 1 H, Ar), 7.957.97 (m, 1 H, Ar), 8.208.26 (m, 6 H, Ph), 8.858.89 (m, 8 H, b-pyrrole-H). 13C NMR (126 MHz, CDCl3): d = 19.83, 20.45, 20.53, 20.63, 61.98, 68.44, 71.42, 72.29, 72.86, 99.41, 116.75, 118.97, 120.28, 120.30, 120.44, 122.95, 126.69, 127.68, 127.78, 129.94, 131.16, 134.54, 142.15, 143.88, 155.41, 169.28, 170.11, 170.27. ESI-HRMS: m/z calcd for C58H49N4O10 + [M + H]+: 961.3443; found: 961.3481. UV/vis (CH2Cl2): lmax (e) = 417 (298600), 515 (18400), 549 (10700), 591 (8700), 646 (6400) nm. 5-[3-(2,3,4,6-Tetraacetyl-b-D- galactosyl)phenyl]- 10,15,20- riphenylporphyrin (4) Yield 116 mg, 84%; mp 169 C. 1H NMR (500 MHz, CDCl3): d = 2.71 (s, 2 H, NH), 1.20 (s, 3 H, OAc), 2.00 (s, 3 H, OAc), 2.10 (s, 3 H, OAc), 2.16 (s, 3 H, OAc), 4.02 (ddd,J = 1.1, 6.4, 6.4 Hz, 1 H, H-5ose), 4.114.14 (m, 2 H, H- 6ose), 5.17 (dd, J = 3.4, 10.4 Hz, 1 H, H-3ose), 5.35 (d, J = 8.0 Hz, 1 H, H-1ose), 5.44 (dd, J = 1.1, 3.4 Hz, 1 H, H- 4ose), 5.64 (dd, J = 8.0, 10.4 Hz, 1 H, H-2ose), 7.477.49 (m, 1 H, Ar), 7.687.71 (m, 1 H, Ar), 7.777.83 (m, 9 H, Ph), 7.947.95 (m, 1 H, Ar), 7.978.00 (m, 1 H, Ar), 8.238.27 (m, 6 H, Ph), 8.878.90 (m, 8 H, b-pyrrole-H). 13C NMR (126 MHz, CDCl3): d = 19.72, 20.48, 20.52, 20.71, 61.45, 67.07, 68.86, 70.92, 71.33, 99.98, 116.70, 118.99, 120.24, 120.28, 120.42, 123.07, 126.68, 127.65, 127.76, 129.91, 131.09, 134.54, 142.14, 143.85, 155.42, 169.32, 169.96, 170.02, 170.09. ESI-HRMS: m/z calcd for C58H49N4O10 + [M + H]+: 961.3443; found: 961.3411. UV/vis (CH2Cl2): lmax (e) = 417 (308600), 515 (20900), 549 (16300), 591 (13600), 646 (10800) nm.
40. Typical Procedure for Deacetylation To a stirred solution of 5-[3-(2,3,4,6-tetraacetyl-b-Dglucosyl) phenyl]-10,15,20-triphenylporphyrin (3a, 50 mg, 0.05 mmol) in dry THFMeOH (1:1, 10 mL) under an argon atmosphere a solution of sodium methanolate in dry MeOH (1.5 mL, 0.02 N) was added. After 2 h the solvent was evaporated under reduced pressure, and the rude product was purified by flash chromatography using CH2Cl2MeOH (9:1) as the eluent. The pure product was obtained as a violet crystalline solid after recrystallization from CH2Cl2MeOH aq. 5 (3-b-D-Glucosylphenyl)-10,15,20-triphenylporphyrin (5a) Yield 40 mg, 97%, mp 160 C. 1H NMR [700 MHz, (CD3)2SO]: d = 2.90 (s, 2 H, NH), 3.223.26 (m, 1 H, Hose), 3.313.38 (m, 3 H, Hose), 3.473.51 (m, 1 H, H- 6Aose), 3.683.71 (m, 1 H, H-6Bose), 4.57 (dd, J = 5.9, 5.9 Hz, 1 H, OH-6ose), 5.01 (d, J = 5.3 Hz, 1 H, OHose), 5.11 (d, J = 5.1 Hz, 1 H, OHose), 5.22 (d, J = 7.6 Hz, 1 H, H-1ose), 5.44 (d, J = 4.9 Hz, 1 H, OHose), 7.537.55 (m, 1 H, Ar), 7.727.75 (m, 1 H, Ar), 7.807.87 (m, 1 H, Ar, 9 H, Ph), 7.917.92 (m, 1 H, Ar), 8.208.24 (m, 6 H, Ph), 8.808.96 (m, 8 H, b-pyrrole-H). 13C NMR [176 MHz, (CD3)2SO]: d = 61.13, 70.17, 73.89, 77.06, 77.47, 100.85, 116.29, 120.01, 120.51, 120.58, 122.87, 127.47, 128.59, 129.00, 134.72, 141.66, 142.87, 156.39. ESI-HRMS: m/z calcd for C50H41N4O6 + [M + H]+: 793.3021; found: 793.2900. UV/vis (CH2Cl2): lmax (e) = 417 (333600), 515 (22800), 549 (16800), 591 (13900), 646 (10700) nm.