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.

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

References

1 The Porphyrin Handbook   Vol 1-20:  Kadish KM. Smith KM. Guilard R. Academic Press; San Diego: 2000-2003. 

2a Binbaum ER. Schaefer WP. Labingev JA. Bercaw JE. Gray HB. Inorg. Chem.  1995,  34:  1751 

2b Campestrini S. Lora G. Tonellato U. Tetrahedron Lett.  2001,  42:  7045 

2c Woller EK. DiMagno SG. J. Org. Chem.  1997,  62:  1588 

2d DiMagno SG. Wertsching AK. Rossa GR. J. Am. Chem. Soc.  1995,  117:  8279 

2e Takeuchi T. Gray HB. Godciardi WA. J. Am. Chem. Soc.  1994,  116:  9730 

2f Moore KT. Fletcher JT. Therin MJ. J. Am. Chem. Soc.  1999,  121:  5196 

2g Taniguchi M. Ra D. Mo G. Balasubramanian T. Lindsey JS. J. Org. Chem.  2001,  66:  7342 

2h Pozzi G. Montanari F. Quici S. Chem. Commun.  1997,  69 

2i Barkigia KM. Battioni P. Riou V. Mansuy D. Fajev J. Chem. Commun.  2002,  956 

3 DiMagno SG. Dussacet PH. Schulty JA. J. Am. Chem. Soc.  1996,  118:  5312 

4a Zeng Z. Liu C. Jin LM. Guo CC. Chen QY. Eur. J. Org. Chem.  2005,  306 

4b Jin LM. Zeng Z. Guo CC. Chen QY. J. Org. Chem.  2003,  68:  3912 

4c Wijesekera TP. Can. J. Chem.  1996,  74:  1868 

4d Goll JG. Moore KT. Ghosh A. Therien MJ. J. Am. Chem. Soc.  1996,  118:  8344 

4e DiMagno SG. Williams RA. Therine MJ. J. Org. Chem.  1994,  59:  6943 

4f Michihide H. Katsuhiro A. Yasuhiro A. Hisanobu O. Tetrahedron Lett.  1983,  24:  4343 

4g Ralph WK. LeGoff E. J. Org. Chem.  1982,  47:  5243 

For recent and selective reports on the transition metal-catalyzed cross-coupling reactions for porphyrin synthesis, see:

5a Gao GY. Colvin AJ. Chen Y. Zhang XP. J. Org. Chem.  2004,  69:  8886 

5b Gao GY. Chen Y. Zhang XP. Org. Lett.  2004,  6:  1837 

5c Gao GY. Colvin AJ. Chen Y. Zhang XP. Org. Lett.  2003,  5:  3261 

5d Gao GY. Chen Y. Zhang XP. J. Org. Chem.  2003,  68:  6215 

5e Chen Y. Zhang XP. J. Org. Chem.  2003,  68:  4432 

5f Takanami T. Hayashi M. Hino F. Suda K. Tetrahedron Lett.  2003,  44:  7353 

5g Khan MM. Ali H. Van Lier JE. Tetrahedron Lett.  2001,  42:  1615 

5h Cheng LL. Chang CJ. Nocera DG. J. Org. Chem.  2003,  68:  4075 

5i Vas B. Alvarez R. Nieto M. Paniello AI. de Lera AR. Tetrahedron Lett.  2001,  42:  7409 

5j Deng Y. Chang CK. Nocera DG. Angew. Chem. Int. Ed.  2000,  39:  1066 

5k Iovine PM. Kellett MA. Redmore NP. Therien MJ. J. Am. Chem. Soc.  2000,  122:  8717 

5l Shanmugathasan S. Johnson CK. Edwards C. Matthews EK. Dolphin D. Boyle RW. J. Porphyrins Phthalocyanines  2000,  4:  228 

5m Shi X. Amin R. Liebeskind LS. J. Org. Chem.  2000,  65:  1650 

5n Sharman WM. Van Lier JE. J. Porphyrins Phthalocyanines  2000,  4:  441 ; and references cited therein

6a Arnold DP. Bott RC. Eldridge H. Elms FM. Smith G. Zojaji M. Aust. J. Chem.  1997,  50:  495 

6b DiMagno SG. Lin VSY. Therien MJ. J. Org. Chem.  1993,  58:  5983 

7 Callot HJ. Bull. Soc. Chim. Fr.  1974,  1492 

8 Kumar DK. Bhyrappa P. Varghese B. Tetrahedron Lett.  2003,  40:  4849 

9 Bhyrappa P. Krishnan V. Inorg. Chem.  1991,  30:  239 

10 McLoughlin VCR. Thrower J. Tetrahedron  1969,  25:  5921 

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.