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Synlett 2009(16): 2701-2705  
DOI: 10.1055/s-0029-1217955
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Partial Bromination and Fluoroalkylation of 5,10,15-Tris(pentafluorophenyl)corrole

Ruo-Bing Du, Chao Liu, Dong-Mei Shen, Qing-Yun Chen*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, 200032 Shanghai, P. R. of China
Fax: +86(21)64166128; e-Mail: chenqy@mail.sioc.ac.cn;
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Publication History

Received 12 May 2009
Publication Date:
04 September 2009 (online)

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Abstract

Partial bromination of the free base of 5,10,15-tris(pentafluorophenyl)corrole was carried out, and various mono-, di-, tri- or tetrabrominated corroles could be selectively produced by controlling the amounts of NBS used. Their consequent Suzuki cross-coupling reactions with arylboronic acids led to various β-substituted corroles in good yields. Fluoroalkylation of the corrole was also studied preliminarily; monofluoroalkylated corrole and five- and six-membered fluorinated ring-fused corroles were synthesized.

Key words

5,10,15-tris(pentafluorophenyl)corrole - partial bromination - Suzuki cross-coupling - fluoroalkylation

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11

General Procedure for the Synthesis of Brominated Corroles: A solution of NBS (1.1 equiv was used for the synthesis of monobrominated corroles 2, 2.1 equiv for dibrominated corrole 3, 3.1 equiv for tribrominated corrole 4, and 4.4 equiv for tetrabrominated corrole 5) in MeCN (10 mL) was added dropwise to corrole 1 (50 mg, 1.0 equiv) dissolved in CH2Cl2 (10 mL) for 8 h at r.t. After the addition was completed, the mixture was stirred for further 30 min. Then, the mixture was subsequently washed with H2O, sat. NaHCO3 and brine. The organic layer was dried over anhyd Na2SO4, filtered, and concentrated under reduced pressure to yield the crude product, which was purified by flash column chromatography. Corrole 3: ¹H NMR (300 MHz, CDCl3): δ = 9.37 (d, J = 4.2 Hz, 1 H), 8.89 (d, J = 4.6 Hz, 1 H), 8.72 (d, J = 4.9 Hz, 1 H), 8.66 (d, J = 4.9 Hz, 1 H), 8.49 (overlapping d, 2 H). ¹9F NMR (CDCl3): δ = -137.66 (dd, ¹ J = 24.2 Hz, ² J = 8.1 Hz, 2 F),
-138.16 (dd, ¹ J = 23.0 Hz, ² J = 6.9 Hz, 2 F), -139.00 (t, J = 19.6 Hz, 2 F), -151.69 (t, J = 20.7 Hz, 2 F), -152.25 (t, J = 20.7 Hz, 1 F), -161.32 (td, ¹ J = 23.0 Hz, ² J = 6.9 Hz, 2 F),
-162.12 (t, J = 18.4 Hz, 4 F). MS (MALDI): m/z = 952.0 [M+]. UV-Vis (CH2Cl2): λ max (rel. int.) = 423 (8), 562 (1.17), 637 (1) nm. HRMS (MALDI): m/z [M+] calcd for C37H9Br2F15N4 +: 951.8949; found: 951.8971.
Corrole 4: ¹H NMR (300 MHz, CDCl3): δ = 9.31 (s, 1 H), 8.82 (d, J = 4.5 Hz, 1 H), 8.69 (d, J = 4.5 Hz, 1 H), 8.62 (d, J = 4.5 Hz, 1 H), 8.52 (d, J = 4.5 Hz, 1 H). ¹9F NMR (CDCl3): δ = -137.88 (dd, ¹ J = 25.0 Hz, ² J = 7.3 Hz, 2 F), -138.20 (br s, 2 F), -139.01 (br s, 2 F), -151.40 (br s, 1 F), -151.64 (t,
J = 22.8 Hz, 1 F), -152.21 (br s, 1 F), -161.28 (dt, ¹ J = 28.2 Hz, ² J = 6.2 Hz, 4 F), -161.91 (br s, 2 F), -162.31 (br s, 2 F). MS (MALDI): m/z = 1029.8 [M+]. UV-Vis (CH2Cl2):
λmax (rel. int.) = 424 (6.77), 570 (1.25), 641 (1) nm. HRMS (MALDI): m/z [M+] calcd for C37H8Br3F15N4 +: 1029.8054; found: 1029.8086. Crystal Data: C38H8Br3F15N4, M = 1033.20, monoclinic, space group C2/c, a = 36.433 (16), b = 12.829 (6), c = 15.844 (7) Å, α = 90˚, β = 109.728 (6)˚, γ = 90˚, V = 6970 (6) ų, T = 293 (2) K, Z = 8, D c = 1.969 g/
cm-³, 10703 reflections measured, 6027 unique which were used in all calculations. R(int) = 0.1667. R 1 = 0.2514. The final wR(F ²) was 0.0895 (all data). CCDC No: 730338.
Corrole 5: ¹H NMR (300 MHz, CDCl3): δ = 8.64 (d, J = 4.8 Hz, 2 H), 8.45 (d, J = 4.8 Hz, 2 H). ¹9F NMR (CDCl3): δ =
-137.60 (dd, ¹ J = 24.2 Hz, ² J = 8.1 Hz, 2 F), -138.48 (dd, ¹ J = 23.0 Hz, ² J = 6.9 Hz, 4 F), -151.52 (d, 3 F), -161.17 (td, ¹ J = 24.2 Hz, ² J = 8.1 Hz, 2 F), -161.94 (td, ¹ J = 23.0, ² J = 6.9 Hz, 4 F). MS (MALDI): m/z = 1029.8 [M+]. UV-Vis (CH2Cl2): λmax (rel. int.) = 424 (6.78), 571 (1.25), 639 (1) nm. HRMS (MALDI): m/z [M+] calcd for C37H7Br4F15N4 +: 1107.7159; found: 1107.7163.

15

General Procedure for Fluoroalkylation of Corrole 1: Corrole 1 (50 mg, 0.06 mmol) was dissolved in DMSO
(5 mL), then Na2S2O4 (54.6 mg, 0.3 mmol) was added. To the mixture a DMSO (5 mL) solution of IC4F8Cl (2.0 equiv) was added dropwise during a period of time (ca. 3-4 h) under nitrogen at r.t. The resulting mixture was stirred for further 2 h. The progress of the reaction was monitored by TLC. After the reaction was finished, the reaction mixture was diluted with CH2Cl2 (20 mL), and washed with H2O (3 ×). The organic layer was dried over anhyd Na2SO4, and concentrated under reduced pressure to dryness. The crude product was purified by flash column chromatography (silica gel, PE-CH2Cl2 = 5:1 as eluent) to provide the desired products. It should be noted that corrole 9a and 9b decomposed slowly during the column chromatography.
Corrole 9a: ¹H NMR (300 MHz, CDCl3): δ = 9.06 (s, 1 H), 8.79 (2 × d, 2 H), 8.70 (d, J = 4.6 Hz, 2 H), 8.57 (d, J = 5.1 Hz, 2 H), 8.51 (d, J = 4.6 Hz, 4 H), 8.48 (d, J = 4.1 Hz, 6 H). ¹9F NMR (CDCl3): δ = -68.45 (s, 2 F), -102.46 (s, 2 F), -119.82 (s, 2 F), -120.50 (s, 2 F), -137.8 to -138.8 (m, 6 F), -152.1 to -153.0 (m, 3 F), -161.6 to -163.8 (m, 6 F). MS (MALDI): m/z = 1120.2 [M+]. UV-Vis (CH2Cl2): λmax (rel. int.) = 420 (13.5), 561 (2.2), 602 (1.4), 637 (1) nm. HRMS (MALDI): m/z [M + H+] calcd for C41H11F23N4Cl+: 1031.0299; found: 1031.0259.