General and Efficient Synthesis of meso- and β-Perfluoroalkylated Porphyrins via Pd-Catalyzed Cross-Coupling Reaction

Abstract

A general and efficient method has been developed for the synthesis of meso- and β-perfluoroalkyl-substituted porphyrins via Pd-catalyzed cross-coupling reaction of meso- and β-brominated porphyrins with perfluoroalkyl iodides and copper.

Key words

brominated porphyrins - AsPh₃ - perfluoroalkylation - Pd₂(dba)₃·CHCl₃

References

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11

General Procedure for the Preparation of MDPP(Rf) ₂ (M3) (M = Ni or Cu).
Porphyrin (40 mg), Pd₂(dba)₃·CHCl₃/AsPh₃ (10 mol%/80 mol%) and Cu (20 equiv to porphyrin) were added to a 50 mL Schlenk flask. The flask was then evacuated and backfilled with argon (three cycles). DMSO (8 mL) and R_fI (10 equiv to porphyrin) were charged with a syringe at r.t. The reaction mixture was stirred at 100 °C for 4-48 h, and then allowed to reach r.t. The reaction mixture was diluted with CH₂Cl₂ and filtered through Celite. The solvent was washed three times with H₂O. The organic layer was dried over Na₂SO₄ and evaporated to dryness. The resulting solid was purified by flash chromatography to yield the desired products in good yields. All the products gave satisfactory spectra. For example, NMR, mass spectra, elemental analysis and UV/Vis spectroscopy data of Ni3a are as follows: ¹H NMR (300 MHz, CDCl₃): δ = 7.64-7.74 (m, 6 H, Ph-H), 7.91 (s, 4 H, Ph-H), 8.76-8.80 (m, 4 H, β-H), 9.24-9.28 (m, 4 H, β-H) ppm. ¹⁹F NMR (282 MHz, CDCl₃): δ = -67.37 (t, J = 14.4 Hz, 4 F, CF₂Cl), -83.13 (br, 4 F, Por-CF₂), -113.37 (s, 4 F, CF ₂CF₂Cl), -119.19 (t, J = 11.3 Hz, 4 F, Por-CF₂CF ₂) ppm. MS (MALDI): m/z = 986.0 [M⁺]. UV/Vis (CH₂Cl₂): λ_max = 411, 543, 585 nm. Anal. Calcd for C₄₈H₁₈N₄F₁₆Cl₂Ni: C, 48.62; H, 1.84; N, 5.67. Found: C, 48.45; H, 2.04; N, 5.57.

12

The perfluoroalkylation of β-bromo-substituted porphyrins were carried out with the starting porphyrin (50 mg), Pd₂(dba)₃·CHCl₃/AsPh₃ (10 mol%/80 mol%), Cu (10 equiv per Br) and IC₄F₈Cl (5 equiv per Br) in 10 mL DMSO at 100 °C for 1-14 h. The procedure was essentially similar to that of perfluoroalkylation of meso-bromo-substituted porphyrins, see ref. 11; the products were characterized on the basis of NMR, mass spectrometry, elemental analysis and UV/Vis spectra. For example, spectroscopic data of Ni8 are as follows: ¹⁹F NMR (282 MHz, CDCl₃): δ = -68.21 (t, J = 12.4 Hz, 4 F, CF₂Cl), -98.23 (m, 4 F, Por-CF₂), -117.44 (m, 4 F, CF ₂CF₂Cl), -119.57 (t, J = 13.5 Hz, 4 F, Por-CF₂CF ₂) ppm. MS (MALDI): m/z = 1138.1 [M⁺]. UV/Vis (CH₂Cl₂): λ_max = 428, 547, 588 nm. Anal. Calcd for C₅₂H₂₆N₄F₁₆Cl₂Ni·H₂O: C, 53.92; H, 2.44; N, 4.84. Found: C, 54.13; H, 2.38; N, 4.77.

13

For the details of this reaction, see ref. 4a; spectroscopic data of Ni11 are as follows: ¹H NMR (300 MHz, CDCl₃): δ = 7.70-7.75 (m, 12 H, Ph-H), 8.01-8.09 (m, 8 H, Ph-H), 8.41 (s, 4 H, β-H) ppm. ¹⁹F NMR (282 MHz, CDCl₃): δ = -131.45 (d, J = 18.6 Hz, 4 F, Por-CF), -156.61 (d, J = 20.0 Hz, 4 F, Por-CF=CF) ppm. MS (MALDI): m/z = 914.1 [M⁺]. UV/Vis (CH₂Cl₂): λ_max = 452, 572, 614 nm. Anal. Calcd for C₅₂H₂₄N₄F₈Ni: C, 68.22; H, 2.64; N, 6.12. Found: C, 68.51; H, 2.71; N, 6.21.