Palladium-Catalysed C2 or C5
Direct Arylation of 3-Substituted Thiophenes with Aryl Bromides

Jia Jia Dong; David Roy; Reny Jacob Roy; Marina Ionita; Henri Doucet

doi:10.1055/s-0030-1260213

PAPER

Palladium-Catalysed C2 or C5 Direct Arylation of 3-Substituted Thiophenes with Aryl Bromides

Jia Jia Dong, David Roy, Reny Jacob Roy, Marina Ionita, Henri Doucet*
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes ‘Catalyse et Organometalliques’, Campus de Beaulieu, 35042 Rennes, France
Fax: +33(2)23236939; e-Mail: henri.doucet@univ-rennes1.fr;

Abstract

Alle Artikel dieser Rubrik

Abstract

The Pd(OAc)₂/dppb system was found to be an efficient catalyst for the direct arylation of 3-substituted thiophene derivatives. The regioselectivity of the arylation strongly depends on the thiophene substituent and also on the nature of the aryl bromide. When using 3-formyl, 3-cyano, 3-methyl, 3-hydroxymethyl or 3-bromothiophene, the 2-arylated thiophenes were obtained with 76-95% regioselectivity; whereas, the arylation of 3-formylthiophene diethylacetal or 3-acetylthiophene gave the 5-arylated thiophenes with 52-90% regioselectivity. The use of congested aryl bromides favours the arylation at C5. These reactions were performed using only 0.1 mol% of catalyst. Moreover, this procedure has been found to be tolerant to a variety of functional groups on the aryl bromide such as formyl, propionyl, benzoyl, nitrile, and nitro.

Key words

catalysis - palladium - thiophenes - arylation - C-H bond activation

Volltext

Referenzen

References

<A NAME="RZ66011SS-1A">1a</A> Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry Pergamon; Amsterdam: 2000.

<A NAME="RZ66011SS-1B">1b</A> Handbook of Organopalladium Chemistry for Organic Synthesis Negishi E. Wiley-Interscience; New York: 2002. Part III. p.213

<A NAME="RZ66011SS-2">2</A> Ohta A. Akita Y. Ohkuwa T. Chiba M. Fukunaga R. Miyafuji A. Nakata T. Tani N. Aoyagi Y. Heterocycles 1990, 31: 1951

<A NAME="RZ66011SS-3A">3a</A> Alberico D. Scott ME. Lautens M. Chem. Rev. 2007, 107: 174

<A NAME="RZ66011SS-3B">3b</A> Satoh T. Miura M. Chem. Lett. 2007, 36: 200

<A NAME="RZ66011SS-3C">3c</A> Campeau L.-C. Stuart DR. Fagnou K. Aldrichimica Acta 2007, 40: 35

<A NAME="RZ66011SS-3D">3d</A> Seregin IV. Gevorgyan V. Chem. Soc. Rev. 2007, 36: 1173

<A NAME="RZ66011SS-3E">3e</A> Li B.-J. Yang S.-D. Shi Z.-J. Synlett 2008, 949

<A NAME="RZ66011SS-3F">3f</A> Mori A. Sugie A. Bull. Chem. Soc. Jpn. 2008, 81: 548

<A NAME="RZ66011SS-3G">3g</A> McGlacken GP. Batman LM. Chem. Soc. Rev. 2009, 38: 2447

<A NAME="RZ66011SS-3H">3h</A> Ackermann L. Vincente R. Kapdi AR. Angew. Chem. Int. Ed. 2009, 48: 9792

<A NAME="RZ66011SS-3I">3i</A> Roger J. Gottumukkala AL. Doucet H. ChemCatChem 2010, 2: 20

<A NAME="RZ66011SS-3J">3j</A> Fischmeister C. Doucet H. Green Chem. 2011, 13: 741

For recent examples of palladium-catalysed direct arylation or vinylation of heteroaromatics with aryl halides from our laboratory, see:

<A NAME="RZ66011SS-4A">4a</A> Gottumukkala AL. Doucet H. Adv. Synth. Catal. 2008, 350: 2183

<A NAME="RZ66011SS-4B">4b</A> Gottumukkala AL. Derridj F. Djebbar S. Doucet H. Tetrahedron Lett. 2008, 49: 2926

<A NAME="RZ66011SS-4C">4c</A> Fall Y. Doucet H. Santelli M. ChemSusChem 2009, 2: 153

<A NAME="RZ66011SS-4D">4d</A> Roger J. Doucet H. Adv. Synth. Catal. 2009, 351: 1977

<A NAME="RZ66011SS-4E">4e</A> Fall Y. Reynaud C. Doucet H. Santelli M. Eur. J. Org. Chem. 2009, 4041

<A NAME="RZ66011SS-4F">4f</A> Dong JJ. Roger J. Pozgan F. Doucet H. Green Chem. 2009, 11: 1832

<A NAME="RZ66011SS-4G">4g</A> Derridj F. Gottumukkala AL. Djebbar S. Doucet H. Eur. J. Inorg. Chem. 2008, 2550

<A NAME="RZ66011SS-4H">4h</A> Roger J. Doucet H. Tetrahedron 2009, 65: 9772

<A NAME="RZ66011SS-4I">4i</A> Roger J. Verrier C. Le Goff R. Hoarau C. Doucet H. ChemSusChem 2009, 2: 951

<A NAME="RZ66011SS-4J">4j</A> Ionita M. Roger J. Doucet H. ChemSusChem 2010, 3: 367

<A NAME="RZ66011SS-4K">4k</A> Fall Y. Doucet H. Santelli M. Synthesis 2010, 127

For selected examples of palladium-catalysed direct arylations of thiophenes, see:

<A NAME="RZ66011SS-5A">5a</A> Penalva V. Lavenot L. Gozzi C. Lemaire M. Appl. Catal., A 1999, 182: 399

<A NAME="RZ66011SS-5B">5b</A> Okazawa T. Satoh T. Miura M. Nomura M. J. Am. Chem. Soc. 2002, 124: 5286

<A NAME="RZ66011SS-5C">5c</A> Masui K. Ikegami H. Mori A. J. Am. Chem. Soc. 2004, 126: 5074

<A NAME="RZ66011SS-5D">5d</A> Masui K. Mori A. Okano K. Takamura K. Kinoshita M. Ikeda T. Org. Lett. 2004, 6: 2011

<A NAME="RZ66011SS-5E">5e</A> Yokooji A. Satoh T. Miura M. Nomura M. Tetrahedron 2004, 60: 6757

<A NAME="RZ66011SS-5F">5f</A> Mitsudo K. Thansandote P. Wilhelm T. Mariampillai B. Lautens M. Org. Lett. 2006, 8: 3939

<A NAME="RZ66011SS-5G">5g</A> Mashraqui SH. Ashraf M. Ghadigaonkar SG. Synlett 2006, 2423

<A NAME="RZ66011SS-5H">5h</A> Amaladass P. Clement JA. Mohanakrishnan AK. Tetrahedron 2007, 63: 10363

<A NAME="RZ66011SS-5I">5i</A> Turner GL. Morris JA. Greaney MF. Angew. Chem. Int. Ed. 2007, 46: 7996

<A NAME="RZ66011SS-5J">5j</A> David E. Pellet-Rostaing S. Lemaire M. Tetrahedron 2007, 63: 8999

<A NAME="RZ66011SS-5K">5k</A> Arai N. Miyaoku T. Teruya S. Mori A. Tetrahedron Lett. 2008, 49: 1000

<A NAME="RZ66011SS-5L">5l</A> Derridj F. Roger J. Geneste F. Djebbar S. Doucet H. J. Organomet. Chem. 2009, 694: 455

<A NAME="RZ66011SS-5M">5m</A> Smaliy RV. Beauperin M. Cattey H. Meunier P. Hierso J.-C. Roger J. Doucet H. Coppel Y. Organometallics 2009, 28: 3152

<A NAME="RZ66011SS-5N">5n</A> Liégault B. Lapointe D. Caron L. Vlassova A. Fagnou K. J. Org. Chem. 2009, 74: 1826

<A NAME="RZ66011SS-5O">5o</A> Roger J. Pozgan F. Doucet H. Green Chem. 2009, 11: 425

<A NAME="RZ66011SS-5P">5p</A> Dong JJ. Roger J. Doucet H. Tetrahedron Lett. 2009, 50: 2778

<A NAME="RZ66011SS-5Q">5q</A> Dong JJ. Roger J. Verrier C. Martin T. Le Goff R. Hoarau C. Doucet H. Green Chem. 2010, 12: 2053

<A NAME="RZ66011SS-5R">5r</A> Derridj F. Roger J. Djebbar S. Doucet H. Org. Lett. 2010, 12: 4320

<A NAME="RZ66011SS-5S">5s</A> Laidaoui N. Miloudi A. El Abed D. Doucet H. Synthesis 2010, 2553

<A NAME="RZ66011SS-5T">5t</A> Beydoun K. Doucet H.
J. Organomet. Chem. 2011, 696: 1749

<A NAME="RZ66011SS-5U">5u</A> Roy D. Mom S. Beaupérin M. Doucet H. Hierso J.-C. Angew. Chem. Int. Ed. 2010, 49: 6650

<A NAME="RZ66011SS-6">6</A> For examples of palladium-catalysed intramolecular direct 2-arylations of 3-substituted thiophenes, see: Mori A. Arai N. Hatta T. Monguchi D. Heterocycles 2010, 80: 103

For examples of palladium-catalysed direct polyarylations of 3-substituted thiophenes, see:

<A NAME="RZ66011SS-7A">7a</A> Nakano M. Tsurugi H. Satoh T. Miura M. Org. Lett. 2008, 10: 1851

<A NAME="RZ66011SS-7B">7b</A> Shibahara F. Yamaguchi E. Murai T. Chem. Commun. 2010, 2471

<A NAME="RZ66011SS-8">8</A> Glover B. Harvey KA. Liu B. Sharp MJ. Tymoschenko MF. Org. Lett. 2003, 5: 301

<A NAME="RZ66011SS-9">9</A> Lavenot L. Gozzi C. Ilg K. Orlova I. Penalva V. Lemaire M. J. Organomet. Chem. 1998, 567: 49

<A NAME="RZ66011SS-10">10</A> Fournier dit Chabert J. Marquez B. Neville L. Joucla L. Broussous S. Bouhours P. David E. Pellet-Rostaing S. Marquet B. Moreau N. Lemaire M. Bioorg. Med. Chem. 2007, 15: 4482

<A NAME="RZ66011SS-11">11</A> Forgione P. Brochu M.-C. St-Onge M. Thesen KH. Bailey MD. Bilodeau F. J. Am. Chem. Soc. 2006, 128: 11350

<A NAME="RZ66011SS-12">12</A> Liégault B. Petrov I. Gorlesky SI. Fagnou K. J. Org. Chem. 2010, 75: 1047

<A NAME="RZ66011SS-13">13</A> Borghese A. Geldhof G. Antoine L. Tetrahedron Lett. 2006, 47: 9249

<A NAME="RZ66011SS-14">14</A> Rene O. Fagnou K. Org. Lett. 2010, 9: 2116

<A NAME="RZ66011SS-15">15</A> Yanagisawa S. Ueda K. Sekizawa H. Itami K. J. Am. Chem. Soc. 2009, 131: 14622

<A NAME="RZ66011SS-16">16</A> Yanagisawa S. Sudo T. Noyori R. Itami K. Tetrahedron 2008, 64: 6073

<A NAME="RZ66011SS-17">17</A> Dong JJ. Doucet H. Eur. J. Org. Chem. 2010, 611

<A NAME="RZ66011SS-18">18</A> Roger J. Pozgan F. Doucet H. Adv. Synth. Catal. 2010, 352: 696

<A NAME="RZ66011SS-19">19</A> Barluenga J. Trincado M. Rubio E. Gonzalez JM. Angew. Chem. Int. Ed. 2006, 45: 3140

<A NAME="RZ66011SS-20">20</A> Roth GP. Farina V. Tetrahedron Lett. 1995, 36: 2191

<A NAME="RZ66011SS-21">21</A> Denton TT. Zhang X. Cashman JR. J. Med. Chem. 2005, 48: 224