Synthesis of Glycoporphyrins by Cross-Metathesis Reactions

Fernando de C da Silva; Vitor F. Ferreira; Maria C. B. V. de Souza; Augusto C. Tomé; Maria G. P. M. S. Neves; Artur M. S. Silva; José A. S. Cavaleiro

doi:10.1055/s-2008-1072718

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Synlett 2008(8): 1205-1207
DOI: 10.1055/s-2008-1072718

LETTER

Synthesis of Glycoporphyrins by Cross-Metathesis Reactions

Fernando de C. da Silva^a,b, Vitor F. Ferreira^b, Maria C. B. V. de Souza^b, Augusto C. Tomé^a, Maria G. P. M. S. Neves^a, Artur M. S. Silva^a, José A. S. Cavaleiro*^a
^a Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Fax: +351(234)370084; e-Mail: jcavaleiro@ua.pt;
^b Departamento de Química Orgânica, Instituto de Química, Universidade Federal Fluminense, 24020-141 Niterói, Rio de Janeiro, Brazil

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Publication History

Received 1 February 2008
Publication Date:
16 April 2008 (online)

Abstract
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Abstract

An easy synthetic approach to glycoporphyrins from zinc(II)-2-vinyl-5,10,15,20-tetraphenylporphyrin or zinc(II)-protoporphyrin-IX dimethyl ester and O-allyl carbohydrate acetonides by cross-metathesis is reported.

Key words

vinylporphyrins - carbohydrate - cross-metathesis - Grubbs catalyst

References and Notes

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9

General Procedure for Glycoporphyrins (6 and 7)
A solution of the metalloporphyrin (0.04 mmol) and Grubbs catalyst 2 (25% mol, 0.01 mmol) in degassed dry CH₂Cl₂ (2 mL) was heated at reflux, under argon, and the allyl sugar 5, dissolved in CH₂Cl₂ (1 mL), was immediately added by a syringe to the mixture. The reflux was kept as mentioned in Table [1] . The solvent was evaporated and the residue was purified by flash chromatography using a gradient of toluene-EtOAc as the eluent. The products 6 and 7 were obtained as red solids after crystallization from PE.
Selected Data for 6a
Mp 171-172 °C. ¹H NMR (300.13 MHz, CDCl₃): δ = 1.30 (s, 3 H, CH₃), 1.47 (s, 3 H, CH₃), 3.27 (s, 3 H, OCH₃), 3.27 (dd, J = 8.3 and 9.7 Hz, 1 H, H-5′a), 3.47 (dd, J = 6.3 and 9.7 Hz, 1 H, H-5′b), 3.87 (dd, J = 2.1 and 5.9 Hz, 2 H, CH ₂CH=CH), 4.22 (dd, J = 6.3 and 8.3 Hz, 1 H, H-4′), 4.52 (d, J = 5.9 Hz, 1 H, H-2′), 4.59 (d, J = 5.9 Hz, 1 H, H-3′), 4.86 (s, 1 H, H-1′), 6.20 (d, J = 15.6 Hz, 1 H, Hb), 6.30 (dt, J = 5.9 and 15.6 Hz, 1 H, Ha), 7.66-7.79 (m, 12 H, ArH), 8.05-8.22 (m, 8 H, Ar ortho), 8.81-8.94 (m, 6 H, H-7, H-8, H-12, H-13, H-17, H-18), 8.95 (d, J = 0.8 Hz, 1 H, H-3). ¹³C NMR (75.47 MHz, CDCl₃): δ = 24.9 (CH₃), 26.4 (CH₃), 54.7 (OCH₃), 70.4 (C-5), 72.2 (CH₂CH=CH), 81.9 (C-3), 84.7 (C-2), 85.0 (C-4), 109.0 (C-1), 112.2 (C-6), 120.5, 121.0, 121.5, 126.5, 126.6, 126.7, 127.3, 127.4, 127.5, 127.8, 129.5 (C-a), 130.9, 131.5, 131.9, 132.0, 132.1, 132.2, 133.8 (C-b), 133.8, 133.9, 134.3, 142.7, 142.9, 146.7, 150.2, 150.3, 150.4, 150.7. UV/Vis (CHCl₃): λ_max (log ε) = 429 (4.57), 559 (4.28), 596.5 (3.63). HRMS (MALDI-TOF): m/z calcd for C₅₆H₄₆N₄O₅Zn [M]⁺: 918.2760; found: 918.2739.
Selected Data for 6b
Mp 165-166 °C. ¹H NMR (300.13 MHz, CDCl₃): δ = 1.32 (s, 3 H, CH₃), 1.36 (s, 3 H, CH₃), 1.48 (s, 3 H, CH₃), 1.51 (s, 3 H, CH₃), 3.60 (dd, J = 6.7 and 10.1 Hz, 1 H, H-6′a), 3.68 (dd, J = 6.7 and 10.1 Hz, 1 H, H-6′b), 3.93-4.05 (m, 1 H, H-5′), 3.93-4.05 (m, 2 H, CHR₂ _RCH=CH), 4.31 (dd, J = 1.9 and 8.0 Hz, 1 H, H-4′), 4.32 (dd, J = 2.5 and 5.0 Hz, 1 H, H-2′), 4.62 (dd, J = 2.5 and 8.0 Hz, 1 H, H-3′), 5.56 (d, J = 5.0 Hz, 1 H, H-1′), 6.22 (d, J = 15.5 Hz, 1 H, Hb), 6.41 (dt, J = 6.3 and 15.5 Hz, 1 H, Ha), 7.68-7.81 (m, 12 H, ArH), 8.06-8.22 (m, 8 H, Ar ortho), 8.82-8.94 (m, 6 H, H-7, H-8, H-12, H-13, H-17, H-18), 8.96 (s, 1 H, H-3). ¹³C NMR (75.47 MHz, CDCl₃): δ = 24.5 (CH₃), 26.9 (CH₃), 26.1 (CH₃), 66.8 (C-5), 68.9 (C-6), 70.6 (C-2), 70.7 (C-3), 71.2 (C-4), 72.8 (CH₂CH=CH), 96.4 (C-1), 108.5 (C-8), 109.2 (C-7), 120.9, 121.2, 121.5, 126.5, 126.9, 127.4, 127.5, 127.9, 129.5 (C-a), 129.7, 131.0, 131.5, 131.9, 132.0, 132.1, 132.3, 133.9 (C-b), 134.4, 142.8, 142.9, 142.7, 143.1, 146.7, 148.6, 150.0, 150.1, 150.2, 150.3, 150.5, 150.8. UV/Vis (CHCl₃): λ_max (log ε) = 429 (4.55), 558.5 (4.25), 599.5 (3.62). HRMS (MALDI-TOF): m/z calcd for C₅₉H₅₀N₄O₆Zn [M]⁺: 974.3022; found: 974.3006.
Selected Data for 6c Mp 190-191 °C. ¹H NMR (300.13 MHz, CDCl₃): δ = 1.32 (s, 3 H, CH₃), 1.36 (s, 3 H, CH₃), 1.38 (s, 3 H, CH₃), 1.54 (s, 3 H, CH₃), 4.06-4.11 (m, 1 H, H-6′a), 4.06-4.11 (m, 1 H, H-6′b), 4.06-4.11 (m, 2 H, CH ₂CH=CH), 4.06-4.11 (m, 1 H, H-3′), 4.16 (dd, J = 2.9 and 7.6 Hz, 1 H, H-4′), 4.30-4.37 (m, 1 H, H-5′), 4.59 (d, J = 3.7 Hz, 1 H, H-2′), 5.93 (d, J = 3.7 Hz, 1 H, H-1′), 6.26 (d, J = 15.6 Hz, 1 H, Hb), 6.36 (dt, J = 5.9 and 15.6 Hz, 1 H, Ha), 7.69-7.80 (m, 12 H, ArH), 8.07-8.21 (m, 8 H, Ar ortho), 8.82-8.93 (m, 6 H, H-7, H-8, H-12, H-13, H-17, H-18), 8.94 (s, 1 H, H-3). ¹³C NMR (75.47 MHz, CDCl₃): δ = 25.4 (CH₃), 26.3 (CH₃), 26.8 (CH₃), 26.9 (CH₃), 67.2 (C-6), 72.5 (C-5), 81.1 (C-4), 81.2 (C-3), 82.9 (C-2), 105.3 (C-1), 108.8 (C-8), 111.8 (C-7), 120.5, 121.1, 126.6, 126.8, 126.9, 127.1, 127.5, 127.6, 127.9, 129.7 (C-a), 130.1, 131.6, 131.9, 132.0, 132.1, 132.3, 133.9, 134.0 (C-b), 134.3, 134.4, 142.7, 142.9, 148.4, 150.1, 150.2, 150.3, 150.8. UV/Vis (CHCl₃): λ_max (log ε) = 429 (4.55), 558.5 (4.26), 595.5 (3.59). HRMS (MALDI-TOF): m/z calcd for C₅₉H₅₀N₄O₆Zn [M]⁺: 974.3022; found: 974.3014.
Selected Data for 7a
Mp 115-116 °C. ¹H NMR (300.13 MHz, CDCl₃): δ = 1.10 (s, 3 H, CH₃), 1.17 (s, 3 H, CH₃), 1.25 (s, 3 H, CH₃), 1.31 (s, 3 H, CH₃), 1.40 (s, 3 H, CH₃), 1.41 (s, 3 H, CH₃), 2.94-3.04 (m, 2 H, CH₂), 3.37 (s, 3 H, CH₃), 3.38 (s, 3 H, CH₃), 3.44 (s, 3 H, CH₃), 3.45 (s, 3 H, CH₃), 3.61 (s, 3 H, OCH₃), 3.61-3.89 (m, 4 H, H-5′), 3.62 (s, 3 H, OCH₃), 3.64 (s, 3 H, OCH₃), 3.74-3.90 (m, 2 H, CH₂), 3.74-3.90 (m, 2 H, CH ₂CH=CH), 3.99-4.14 (m, 4 H, CH₂), 4.57 (d, J = 5.9 Hz, 1 H, H-2′) and 4.62 (d, J = 5.9 Hz, 1 H, H-2′), 4.67-4.73 (m, 2 H, H-4′), 4.91 (d, J = 5.9 Hz, 1 H, H-3′) and 4.93 (d, J = 5.9 Hz, 1 H, H-3′), 5.04 (s, 1 H, H-1′) and 5.06 (s, 1 H, H-1′), 6.12 (dt, J = 5.9 and 17.5 Hz, 1 H, Ha) and 6.11 (dt, J = 5.9 and 17.5 Hz, 1 H, Ha), 6.24 (d, J = 17.5 Hz, 1 H, Ha) and 6.23 (d, J = 17.5 Hz, 1 H, Ha), 9.30 (s, 1 H, H_meso), 9.26 (s, 1 H, H_meso), 9.17 (s, 1 H, H_meso), 9.11 (s, 1 H, H_meso). ¹³C NMR (75.47 MHz, CDCl₃): δ = 11.4, 11.5, 12.4 and 12.5 (4 × CH₃), 21.6 (CH₂), 24.9 and 26.4 (CH₃ of isopropylidene), 36.8 (CH₂), 51.6 (CO₂OCH₃), 54.7 and 54.8 (OCH₃), 71.1 (C-5′), 76.6 (CH₂CH=CH), 77.4 (C-4′), 82.1 (C-5′), 85.0 and 85.1 (C-2′), 95.4, 96.5, 97.9 and 97.2 (CH in 5, 10, 15, 20 positions), 109.2 and 109.3 (C-1′), 112.3 (C-6′), 119.0 and 119.1, 129.2, 130.3 and 130.5, 135.3, 135.9, 136.0, 136.1, 136.4, 137.8, 138.0, 144.9, 145.6, 145.7, 145.9, 146.0, 146.1, 146.2, 146.4, 147.0, 147.1, 173.3 (C=O). UV/Vis (CHCl₃): λ_max (log ε) = 415.5 (5.36), 544 (4.20), 580.5 (4.28). HRMS (MALDI-TOF): m/z calcd for C₅₆H₆₈N₄O₁₄Zn [M]⁺: 1084.4023; found: 1084.4007.