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.

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

References and Notes

<A NAME="RU05111ST-1A">1a</A> Brunner H. Schellerer KM. Monatsh. Chem.  2002,  133:  679 

<A NAME="RU05111ST-1B">1b</A> Harsat A. Van Lier JE. Chem. Rev.  1999,  99:  2379 

<A NAME="RU05111ST-1C">1c</A> Bonnett R. White RD. Winfield U.-J. Berenbaum MC. Biochem. J.  1989,  261:  277 

<A NAME="RU05111ST-2A">2a</A> Anderson HL. Chem. Commun.  1999,  2323 

<A NAME="RU05111ST-2B">2b</A> Kim D. Osuka A. J. Phys. Chem. A.  2003,  107:  8791 

<A NAME="RU05111ST-3A">3a</A> Anderson HL. Martin SJ. Bradley DCC. Angew. Chem., Int. Ed. Engl.  1994,  33:  655 

<A NAME="RU05111ST-3B">3b</A> Martin SJ. Anderson HL. Bradley DCC. Adv. Mater. Opt. Electron.  1994,  4:  277 

<A NAME="RU05111ST-3C">3c</A> Anderson HL. Brédas JL. J. Chem. Phys.  1997,  106:  9439 

<A NAME="RU05111ST-4A">4a</A> LeCours SM. Guan H.-W. DiMagno SG. Wang CH. Therien MJ. J. Am. Chem. Soc.  1996,  118:  1497 

<A NAME="RU05111ST-4B">4b</A> Priyadarshy S. Therien MJ. Beratan DN. J. Am. Chem. Soc.  1996,  118:  1504 

<A NAME="RU05111ST-5">5</A> Lin VS.-Y. DiMagno SG. Therien MJ. Science  1994,  264:  1105 

<A NAME="RU05111ST-6A">6a</A> Guo XM. J. Mol. Struct.  2008,  892:  378 

<A NAME="RU05111ST-6B">6b</A> Zhu L.-J. Wang J. Reng T.-G. Li C.-Y. Guo D.-C. Guo C.-C. J. Phys. Org. Chem.  2010,  23:  190 

<A NAME="RU05111ST-7A">7a</A> Zhou X. Tse MK. Wan TSM. Chan KS. J. Org. Chem.  1996,  61:  3590 

<A NAME="RU05111ST-7B">7b</A> Cammidge AN. Öztürk O. J. Org. Chem.  2002,  67:  7457 

<A NAME="RU05111ST-7C">7c</A> Plater MJ. Aiken S. Bourhill G. Tetrahedron  2002,  58:  2405 

<A NAME="RU05111ST-8A">8a</A> Lin VS.-Y. DiMagno SG. Therien MJ. Chem. Eur. J.  1995,  1105 

<A NAME="RU05111ST-8B">8b</A> Anderson HL. Wylie AP. Prout K.
J. Chem. Soc., Perkin Trans. 1  1998,  1607 

<A NAME="RU05111ST-8C">8c</A> Angiolillo PJ. Uyeda HT. Duncan TV. Therien MJ. J. Phys. Chem. B  2004,  108:  11893 

<A NAME="RU05111ST-8D">8d</A> Ostrowski JC. Susumu K. Robinson MR. Therien MJ. Bazan GC. Adv. Mater.  2003,  15:  1296 

<A NAME="RU05111ST-8E">8e</A> Arnold DP. Heath GA. James DA. J. Porphyrins Phthalocyanines  1999,  3:  5 

<A NAME="RU05111ST-8F">8f</A> Wytko J. Berl V. McLaughlin M. Tykwinski RR. Schreiber M. Diederich F. Helv. Chim. Acta  1998,  81:  1964 

<A NAME="RU05111ST-8G">8g</A> Susumu K. Maruyama H. Kobayashi H. Tanaka K. J. Mater. Chem.  2001,  11:  2262 

<A NAME="RU05111ST-9A">9a</A> Kuninubu Y. Nishina Y. Nakagawa C. Takai K.
J. Am. Chem. Soc.  2006,  128:  12376 

<A NAME="RU05111ST-9B">9b</A> Kuninubu Y. Nishina Y. Takai K. Tetrahedron  2007,  63:  8463 

<A NAME="RU05111ST-10A">10a</A> Kuninubu Y. Takata H. Kawata A. Takai K. Org. Lett.  2008,  10:  3133 

<A NAME="RU05111ST-10B">10b</A> Kuninobu Y. Nishi M. Kawata A. Takata H. Hanatani Y. Yudha SS. Iwai A. Takai K. J. Org. Chem.  2010,  75:  334 

<A NAME="RU05111ST-10C">10c</A> Kuninobu Y. Iwanaga T. Nishi M. Takai K. Chem. Lett.  2010,  39:  894 

<A NAME="RU05111ST-10D">10d</A> Kuninobu Y. Seiki T. Kanamaru S. Nishina Y. Takai K. Org. Lett.  2010,  12:  5287 

<A NAME="RU05111ST-11">11</A> Anderson HL. Tetrahedron Lett.  1992,  33:  1101 

<A NAME="RU05111ST-12A">12a</A> Yen W.-N. Lo S.-S. Kuo M.-C. Mai C.-L. Lee G.-H. Peng S.-M. Yeh C.-Y. Org. Lett.  2006,  8:  4239 

<A NAME="RU05111ST-12B">12b</A> Kuo M.-C. Li L.-A. Yen W.-N. Lo S.-S. Lee C.-W. Yeh C.-Y. Dalton Trans.  2007,  1433 

<A NAME="RU05111ST-13">13</A>

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.

<A NAME="RU05111ST-14">14</A>

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.