Direct Arylation of Heteroarenes
Catalyzed by a Palladium-1,10-Phenanthroline
Complex

Ryo Takita; Daichi Fujita; Fumiyuki Ozawa

doi:10.1055/s-0030-1259727

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Synlett 2011(7): 959-963
DOI: 10.1055/s-0030-1259727

LETTER

Direct Arylation of Heteroarenes Catalyzed by a Palladium-1,10-Phenanthroline Complex

Ryo Takita*^a,b, Daichi Fujita^a, Fumiyuki Ozawa*^a
^a International Research Center for Elements Science (IRCELS), Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Fax: +81(774)383039; e-Mail: ozawa@scl.kyoto-u.ac.jp;
^b Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
e-Mail: takita@mol.f.u-tokyo.ac.jp;

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Publication History

Received 10 December 2010
Publication Date:
10 March 2011 (online)

Abstract
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Abstract

A new entry in direct arylation of heteroarenes using Pd(OAc)₂ and 1,10-phenanthroline as a nitrogen-based ligand is reported. The long induction period observed at the initial stage of the reaction was effectively reduced by modification of the catalyst preparation, leading to improved chemical yields (69-92%) and shortening of reaction times (3-10 h).

Key words

direct arylation - palladium - 1,10-phenanthroline - heteroarenes - biaryls

Supporting Information

References and Notes

For recent reviews on direct arylation or functionalization of aryl C-H bonds, see:
1a Alberico D. Scott ME. Lautens M. Chem. Rev. 2007, 107: 174

Google Scholar
1b Satoh T. Miura M. Chem. Lett. 2007, 36: 200

Google Scholar
1c Seregin IV. Gevorgyan V. Chem. Soc. Rev. 2007, 36: 1173

Google Scholar
1d Campeau L.-C. Stuart DR. Fagnou K. Aldrichimica Acta 2007, 40: 35

Google Scholar
1e Mori A. Sugie A. Bull. Chem. Soc. Jpn. 2008, 81: 548

Google Scholar
1f Kakiuchi F. Kochi T. Synthesis 2008, 3013

Google Scholar
1g Lewis JC. Bergman RG. Ellman JA. Acc. Chem. Res. 2008, 41: 1013

Google Scholar
1h Li B.-J. Yang S.-D. Shi Z.-J. Synlett 2008, 949

Google Scholar
For pioneering works on direct arylation of heteroarenes, see:
2a Nakamura N. Tajima Y. Sakai K. Heterocycles 1982, 17: 235

Google Scholar
2b Akita Y. Itagaki Y. Takizawa S. Ohta A. Chem. Pharm. Bull. 1989, 37: 1477

Google Scholar
2c Ohta A. Akita Y. Ohkuwa T. Chiba M. Fukunaga R. Miyafuji A. Nakata T. Tani N. Aoyagi Y. Heterocycles 1990, 31: 1951

Google Scholar
For pioneering works on direct functionalization of arenes, see:
3a Jia C. Kitamura T. Fujiwara Y. Acc. Chem. Res. 2001, 34: 633

Google Scholar
3b Shilov AE. Shul’pin GB. Chem. Rev. 1997, 97: 2879

Google Scholar
For representative examples of palladium-catalyzed reactions, see:
5a Pivsa-Art S. Satoh T. Kawamura Y. Miura M. Nomura M. Bull. Chem. Soc. Jpn. 1998, 71: 467

Google Scholar
5b Sévignon M. Papillon J. Schulz E. Lemaire M. Tetrahedron Lett. 1999, 40: 5873

Google Scholar
5c Okazawa T. Satoh T. Miura M. Nomura M. J. Am. Chem. Soc. 2002, 124: 5286

Google Scholar
5d Hassan J. Schulz E. Gozzi C. Lemaire M.
J. Mol. Catal. A: Chem. 2003, 195: 121

Google Scholar
5e Glover B. Harvery KA. Liu B. Sharp MJ. Tymoschenko MF. Org. Lett. 2003, 5: 301

Google Scholar
5f Mori A. Sekiguchi A. Masui K. Shimada T. Horie M. Osakada K. Kawamoto M. Ikeda T. J. Am. Chem. Soc. 2003, 125: 1700

Google Scholar
5g Masui K. Ikegami H. Mori A. J. Am. Chem. Soc. 2004, 126: 5074

Google Scholar
5h Park C.-H. Ryabova V. Seregin IV. Sromek AW. Gevorgyan V. Org. Lett. 2004, 6: 1159

Google Scholar
5i Lane BS. Sames D. Org. Lett. 2004, 6: 2897

Google Scholar
5j Lane BS. Sames D. J. Am. Chem. Soc. 2005, 127: 8050

Google Scholar
5k Bressy C. Alberico D. Lautens M. J. Am. Chem. Soc. 2005, 127: 13148

Google Scholar
5l Kobayashi K. Sugie A. Takahashi M. Masui K. Mori A. Org. Lett. 2005, 7: 5083

Google Scholar
5m Campeau L.-C. Rousseaux S. Fagnou K. J. Am. Chem. Soc. 2005, 127: 18020

Google Scholar
5n Touré BB. Lane BS. Sames D. Org. Lett. 2006, 8: 1979

Google Scholar
5o Deprez NR. Kalyani D. Krause A. Sanford MS. J. Am. Chem. Soc. 2006, 128: 4972

Google Scholar
5p Nakano M. Satoh T. Miura M. J. Org. Chem. 2006, 71: 8309

Google Scholar
5q Bellina F. Cauteruccio S. Rossi R. Eur. J. Org. Chem. 2006, 1379

Google Scholar
5r Battace A. Lemhadri M. Zair T. Doucet H. Santelli M. Organometallics 2007, 26: 472

Google Scholar
5s Wang X. Gribkov DV. Sames D. J. Org. Chem. 2007, 72: 1476

Google Scholar
5t Chiong HA. Daugulis O. Org. Lett. 2007, 9: 1449

Google Scholar
5u Chuprakov S. Chernyak N. Dudnik AS. Gevorgyan V. Org. Lett. 2007, 9: 2333

Google Scholar
5v Iwasaki M. Yorimitsu H. Oshima K. Chem. Asian J. 2007, 2: 1430

Google Scholar
5w Bellina F. Cauteruccio S. Rossi R. J. Org. Chem. 2007, 72: 8543

Google Scholar
5x Turner GL. Morris JA. Greaney MF. Angew. Chem. Int. Ed. 2007, 46: 7996

Google Scholar
5y Larivée A. Mousseau JJ. Charette AB. J. Am. Chem. Soc. 2008, 130: 52

Google Scholar
5z Labrasseur N. Larrosa I.
J. Am. Chem. Soc. 2008, 130: 2926

Google Scholar
6a Campeau L.-C. Bertrand-Laperle M. Leclerc J.-P. Villemure E. Gorelsky S. Fagnou K. J. Am. Chem. Soc. 2008, 130: 3276

Google Scholar
6b Bellina F. Benelli F. Rossi R.
J. Org. Chem. 2008, 73: 5529

Google Scholar
6c Nakano M. Tsurugi H. Satoh T. Miura M. Org. Lett. 2008, 10: 1851

Google Scholar
6d Flegeau EF. Popkin ME. Greaney MF. Org. Lett. 2008, 10: 2717

Google Scholar
6e Gorelsky SI. Lapointe D. Fagnou K. J. Am. Chem. Soc. 2008, 130: 10848

Google Scholar
6f Verrier C. Martin T. Hoarau C. Marsais F. J. Org. Chem. 2008, 73: 7383

Google Scholar
6g Martin T. Verrier C. Hoarau C. Marsais F. Org. Lett. 2008, 10: 2909

Google Scholar
6h Martins A. Lautens M. J. Org. Chem. 2008, 73: 8705

Google Scholar
6i Ackermann L. Althammer A. Fenner S. Angew. Chem. Int. Ed. 2009, 48: 201

Google Scholar
6j Roger J. Pozgan F. Doucet H. J. Org. Chem. 2009, 74: 1179

Google Scholar
6k Liégault B. Lapointe D. Caron L. Vlassova A. Fagnou K. J. Org. Chem. 2009, 74: 1826

Google Scholar
6l Goikhman R. Jacques TL. Sames D. J. Am. Chem. Soc. 2009, 131: 3042

Google Scholar
6m Campeau L.-C. Stuart DR. Leclerc J.-P. Bertrand-Laperle M. Villemure E. Sun H.-Y. Lasserre S. Guimond N. Lecavallier M. Fagnou K. J. Am. Chem. Soc. 2009, 131: 3291

Google Scholar
6n Huestis MP. Fagnou K. Org. Lett. 2009, 11: 1357

Google Scholar
6o Masuda N. Tanba S. Sugie A. Monguchi D. Koumura N. Hara K. Mori A. Org. Lett. 2009, 11: 2297

Google Scholar
6p Zhang Y.-H. Shi B.-F. Yu J.-Q. J. Am. Chem. Soc. 2009, 131: 5072

Google Scholar
6q Yanagisawa S. Ueda K. Sekizawa H. Itami K. J. Am. Chem. Soc. 2009, 131: 14622

Google Scholar
6r Xi P. Yang F. Qin S. Zhao D. Lan J. Gao G. Hu C. You J. J. Am. Chem. Soc. 2010, 132: 1822

Google Scholar
6s René O. Fagnou K. Adv. Synth. Catal. 2010, 352: 2116

Google Scholar
6t Ueda K. Yangisawa S. Yamgauchi J. Itami K. Angew. Chem. Int. Ed. 2010, 49: 8946

Google Scholar
6u Sun H.-Y. Gorelsky SI. Stuart DR. Campeau L.-C. Fagnou K.
J. Org. Chem. 2010, 75: 8180

Google Scholar
For rhodium-catalyzed reactions, see:
7a Lewis JC. Wiedemann SH. Bergmann RG. Ellman JA. Org. Lett. 2004, 6: 35

Google Scholar
7b Wang X. Lane BS. Sames D.
J. Am. Chem. Soc. 2005, 127: 4996

Google Scholar
7c Wiedemann SH. Lewis JC. Ellman JA. Bergmann RG. J. Am. Chem. Soc. 2006, 128: 2452

Google Scholar
7d Lewis JC. Wu JY. Bergmann RG. Ellman JA. Angew. Chem. Int. Ed. 2006, 45: 1589

Google Scholar
7e Yanagisawa S. Sudo T. Noyori R. Itami K. J. Am. Chem. Soc. 2006, 128: 11748

Google Scholar
7f Yanagisawa S. Sudo T. Noyori R. Itami K. Tetrahedron 2008, 64: 6073

Google Scholar
7g Lewis JC. Berman AM. Bergmann RG. Ellman JA. J. Am. Chem. Soc. 2008, 130: 2493

Google Scholar
7h Berman AM. Lewis JC. Bergmann RG. Ellman JA. J. Am. Chem. Soc. 2008, 130: 14926

Google Scholar
For copper-catalyzed reactions, see:
8a Do H.-Q. Daugulis O. J. Am. Chem. Soc. 2007, 129: 12404

Google Scholar
8b Do H.-Q. Khan RMK. Daugulis O. J. Am. Chem. Soc. 2008, 130: 15185

Google Scholar
8c Ackermann L. Potukuchi HK. Landsberg D. Vicente R. Org. Lett. 2008, 10: 3081

Google Scholar
8d Yoshizumi T. Tsurugi H. Satoh T. Miura M. Tetrahedron Lett. 2008, 49: 1598

Google Scholar
For direct arylation of heteroarenes promoted by other metal species, see:
9a Yanagisawa S. Ueda K. Taniguchi T. Itami K. Org. Lett. 2008, 10: 4673

Google Scholar
9b Caniviet J. Yamaguchi J. Ban I. Itami K. Org. Lett. 2009, 11: 1733

Google Scholar
9c Hachiya H. Hirano K. Satoh T. Miura M. Org. Lett. 2009, 11: 1737

Google Scholar
9d Join B. Yamamoto T. Itami K. Angew. Chem. Int. Ed. 2009, 48: 3644

Google Scholar
9e Liu W. Cao H. Lei A. Angew. Chem. Int. Ed. 2010, 49: 2004

Google Scholar
9f Vallée F. Mousseau JJ. Charrette AB. J. Am. Chem. Soc. 2010, 132: 1514

Google Scholar
10 Palladium-catalyzed polycondensation of 2-bromothio-phenes based on direct arylation has been recently developed, see: Wang Q. Takita R. Kikuzaki Y. Ozawa F. J. Am. Chem. Soc. 2010, 132: 11420

Crossref Google Scholar
11 Deprez NR. Sanford MS. Inorg. Chem. 2007, 46: 1924

Crossref PubMed Google Scholar
12a Biswas B. Sugimoto M. Sakaki S. Organometallics 2000, 19: 3895

Google Scholar
12b Davies DL. Donald SMA. Macgregor SA. J. Am. Chem. Soc. 2005, 127: 13754

Google Scholar
12c Garcia-Cuadrado D. de Mendoza P. Braga AAC. Maseras F. Echavarren AM. J. Am. Chem. Soc. 2007, 129: 6880

Google Scholar
12d Lafrance M. Lapointe D. Fagnou K. Tetrahedron 2008, 64: 6015

Google Scholar
12e Pascual S. de Mendoza P. Braga AAC. Maseras F. Echavarren AM. Tetrahedron 2008, 64: 6021 ; and references cited therein

Google Scholar
A stoichiometric reaction of [Pd(aryl)I(bipy)] with thiophene in the presence of AgNO₃ and KF to afford 2-arylthiophene has been reported by Mori et. al:
13a Sugie A. Kobayashi K. Suzaki Y. Osakada K. Mori A. Chem. Lett. 2006, 35: 1100

Google Scholar
13b Mori A. Sugie A. Furukawa H. Suzaki Y. Osakada K. Akita M. Chem. Lett. 2008, 37: 542

Google Scholar
13c Sugie A. Furukawa H. Suzaki Y. Osakada K. Akita M. Monguchi D. Mori A. Bull. Chem. Soc. Jpn. 2009, 82: 555

Google Scholar
Cleavage of arene C-H bonds on platinum(II) diimine complexes has been reported:
14a Lersch M. Tilset M. Chem. Rev. 2005, 105: 2471

Google Scholar
14b Wik BJ. Lersch M. Krivokapic A. Tilset M. J. Am. Chem. Soc. 2006, 128: 2682

Google Scholar
14c Williams TJ. Labinger JA. Bercaw JE. Organometallics 2007, 26: 281

Google Scholar
14d Williams TJ. Caffyn AJM. Hazari N. Oblad PF. Labinger JA. Bercaw JE. J. Am. Chem. Soc. 2008, 130: 2418

Google Scholar
14e Bercaw JE. Hazari N. Labinger JA. Oblad PF. Angew. Chem. Int. Ed. 2008, 47: 9941 ; and references cited therein

Google Scholar
15 Very recently, Shibahara, Murai and co-workers reported a related catalytic system using [Pd^II(1,10-phenanthro-line)₂](PF₆)₂, see: Shibahara F. Yamaguchi E. Murai T. Chem. Commun. 2010, 46: 2471

Crossref Google Scholar
In contrast, Pd(OAc)₂ is known to be reduced smoothly to a Pd(0) species in the presence of tertiary phosphine ligands:
18a Ozawa F. Kubo A. Hayashi T. Chem. Lett. 1992, 21: 2177

Google Scholar
18b Amatore C. Jutand A. M’Barki MA. Organometallics 1992, 11: 3009

Google Scholar
18c Amatore C. Carre E. Jutand A. M’Barki MA. Organometallics 1995, 14: 1818

Google Scholar

4

In this manuscript, the term ‘direct arylation of heteroarenes’ denotes the reaction of heteroarenes with (pseudo)halo-arenes. For other types of reactions (e.g., directing-group-controlled reactions or the reaction of arenes with organometallic reagents), see ref. 1.

16

Isolated Pd(OAc)₂(1,10-phenanthroline) gave a comparable result (69%) under the same conditions.

17

The remaining part of 1a is very probably converted to benzene. The reduction of 1e to give ethyl benzoate was confirmed by GC-MS analysis of the reaction solution of entry 5 in Table [²] .

Supplementary Material

Supporting Information