Synthesis of meso-Substituted Tetraarylalkynylporphyrins via Rhenium-Catalyzed Formation of Naphthalene Units

Abstract

Rhenium-catalyzed synthesis of naphthalene-substituted aryl bromides or iodides via C-H bond activation, and its use for palladium-catalyzed cross-coupling reactions with tetraethynylporphyrin are described. A series of novel meso-substituted tetraalkynylporphyrins with naphthalene moieties were obtained.

Key words

rhenium catalyst - C-H bond activation - naphthalene derivative - Sonogashira coupling - meso-substituted tetraalkynyl­porphyrin

References and Notes

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13

General Procedure for the Synthesis of Naphthalene Derivatives 6 by One-Pot Reaction A mixture of N-(diphenylmethylene)aniline (1, 129 mg, 0.500 mmol), 4-bromobenzaldehyde (2a, 1.00 mmol) or 4-iodobenzaldehyde (2b, 1.00 mmol), olefin (4, 0.600 mmol), 4 Å MS (200 mg), [ReBr(CO)₃(thf)]₂ (10.6 mg, 0.0125 mmol), and toluene (1.0 mL) was stirred at 115 ˚C for 48 h. Then, AcOH (3.0 mL) and H₂SO₄ (1.0 mL) were added, and the mixture was stirred at r.t. for 2 h. The crude product was extracted with hexane and purified by column chromatography on silica gel or recrystallized from EtOH to give naphthalene derivative 6.

14

Typical Procedure for the Synthesis of meso -Substituted Tetraarylalkynylporphyrin 9a Porphyrins 7 ^¹¹ and 8 ^¹²a were prepared according to the reported methods. To a degassed solution of zinc(II) 5,10,15,20-tetraethynylporphyrin (8, 10 mg, 0.021 mmol), 1-(4-iodophenyl)-4-phenylnaphthalene-2,3-dicarboxylic acid diethyl ester (6d, 75.4 mg, 0.137 mmol), and AsPh₃ (12 mg, 0.038 mmol) in a mixture of anhyd THF (10 mL) and Et₃N (5.0 mL) was added Pd₂(dba)₃ (2.0 mg, 0.0020 mmol). The reaction mixture was stirred at 50 ˚C for 4 h under an argon atmosphere. The solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography on silica gel using CHCl₃ as an eluent to give a dark green solid 9a (41.7 mg, 92%). ^¹H NMR (400 MHz, CDCl₃): δ = 0.96 (t, J = 7.2 Hz, 12 H), 1.17 (t, J = 7.2 Hz, 12 H), 4.03 (q, J = 7.2 Hz, 8 H), 4.19 (q, J = 7.2 Hz, 8 H), 7.43-7.55 (m, 28 H), 7.68-7.71 (m, 12 H), 7.85 (d, J = 8.4 Hz, 4 H), 8.27 (d, J = 8.0 Hz, 8 H), 9.48 (s, 8 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 13.6, 13.9, 61.4, 61.6, 66.7, 92.8, 96.9, 102.7, 123.7, 127.1, 127.5, 127.8, 127.9, 128.1, 129.0, 129.2, 130.2, 130.7, 131.2, 131.5, 132.6, 132.8, 137.7, 138.3, 138.4, 139.3, 151.3, 168.3, 168.4. IR (Nujol): 480, 771, 941, 1132, 1166, 1222, 1300, 1676, 1685, 1716, 1734, 2213, 2924 cm^-¹.