N-Heterocyclic Carbene-Palladium(II)-1-Methylimidazole Complex Catalyzed α-Arylation of Ketones with Aryl Chlorides

Abstract

An easily available NHC-Pd(II)-Im (NHC = N-heterocyclic carbene, Im = 1-methylimidazole) complex was found to be an efficient catalyst for the α-arylation reaction between ketones and aryl chlorides. Under the optimal conditions, all reactions proceeded smoothly to give the desired products in good to high yields within hours.

Key words

N-heterocyclic carbenes - palladium - α-arylation - aryl chlorides - ketones

References

• 1a Tsuji J. Palladium Reagents and Catalysis: Innovations in Organic Synthesis   Wiley; New York: 1995. 
• 1b Metal-Catalyzed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998. 
• 1c Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E.-i. de Meijere A. John Wiley & Sons; New York: 2002. 
• 1d Metal-Catalyzed Cross-Coupling Reactions   Vols. 1 and 2:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
• For some initial examples, see:
• 2a Fauvarque JF. Jutand A. J. Organomet. Chem.  1979,  177:  273 
• 2b Galarini R. Musco A. Pontellini R. Santi R. J. Mol. Catal.  1992,  72:  L11 
• 2c Kuwajima I. Nakamura E.-i. Acc. Chem. Res.  1985,  18:  181 
• 2d Kosugi M. Hagiwara I. Sumiya T. Migita T. Bull. Chem. Soc. Jpn.  1985,  58:  3383 
• For some selected examples using ketones as the substrate, see:
• 3a Palucki M. Buchwald SL. J. Am. Chem. Soc.  1997,  119:  11108 
• 3b Hamann BC. Hartwig JF. J. Am. Chem. Soc.  1997,  119:  12382 
• 3c Satoh T. Kawamura Y. Miura M. Nomura M. Angew. Chem., Int. Ed. Engl.  1997,  36:  1740 
• 3d Culkin DA. Hartwig JF. Acc. Chem. Res.  2003,  36:  234 
• 3e Huang J.-K. Bunel E. Faul MM. Org. Lett.  2007,  9:  4343 
• 3f Hama T. Hartwig JF. Org. Lett.  2008,  10:  1545 
• 3g Hama T. Hartwig JF. Org. Lett.  2008,  10:  1549 
• 3h Biscoe MR. Buchwald SL. Org. Lett.  2009,  11:  1773 
• 3i Liao X.-B. Weng Z.-Q. Hartwig JF. J. Am. Chem. Soc.  2008,  130:  195 
• 3j Miura M. Satoh T. In Palladium in Organic Synthesis   Vol. 14:  Tsuji J. Springer; Berlin: 2005. 
• For reviews of NHC-palladium complexes in coupling reactions, see:
• 4a Hillier AC. Grasa GA. Viciu MS. Lee HM. Yang C.-L. Nolan SP. J. Organomet. Chem.  2002,  653:  69 
• 4b Kantchev EAB. O’Brien CJ. Organ MG. Angew. Chem. Int. Ed.  2007,  46:  2768 
• 4c Marion N. Nolan SP. Acc. Chem. Res.  2008,  41:  1440 
• 4d Fortman GC. Nolan SP. Chem. Soc. Rev.  2011,  40:  5151 
• For Nolan’s contributions, see:
• 5a Viciu MS. Germaneau RF. Nolan SP. Org. Lett.  2002,  4:  4053 
• 5b Viciu MS. Kelly RA. Stevens ED. Naud F. Studer M. Nolan SP. Org. Lett.  2003,  5:  1479 
• 5c Navarro O. Marion N. Scott NM. González J. Amoroso D. Bell A. Nolan SP. Tetrahedron  2005,  61:  9716 
• 5d Navarro O. Marion N. Oonishi Y. Kelly RA. Nolan SP. J. Org. Chem.  2006,  71:  685 
• 5e Marion N. Ecarnot EC. Navarro O. Amoroso D. Bell A. Nolan SP. J. Org. Chem.  2006,  71:  3816 
• 5f Marion N. de Frémont P. Puijk IM. Ecarnot EC. Amoroso D. Bell A. Nolan SP. Adv. Synth. Catal.  2007,  349:  2380 
• For the contributions of some others, see:
• 6a Lee S. Beare NA. Hartwig JF. J. Am. Chem. Soc.  2001,  123:  8410 
• 6b Kündig EP. Seidel TM. Jia Y.-X. Bernardinelli G. Angew. Chem. Int. Ed.  2007,  46:  8484 
• 6c Cao C.-S. Wang L.-L. Cai Z.-Y. Zhang L.-Q. Guo J. Pang G.-S. Shi Y.-H. Eur. J. Org. Chem.  2011,  1570 
• 6d Zhang J.-L. Yang X.-Q. Cui X.-L. Wu Y.-J. Tetrahedron  2011,  67:  8800 
• 7a Zhu L. Gao T.-T. Shao L.-X. Tetrahedron  2011,  67:  5150 
• 7b Zhou X.-X. Shao L.-X. Synthesis  2011,  3138 
• 7c Tang Y.-Q. Lu J.-M. Shao L.-X. J. Organomet. Chem.  2011,  696:  3741 
• 7d Gu Z.-S. Shao L.-X. Lu J.-M. J. Organomet. Chem.  2012,  700:  132 
• 8 Lundin PM. Esquivias J. Fu GC. Angew. Chem. Int. Ed.  2009,  48:  154 
• 9 Lubczyk V. Bachmann H. Gust R. J. Med. Chem.  2003,  46:  1484 
• 10 Ackermann L. Spatz JH. Gschrei CJ. Born R. Althammer A. Angew. Chem. Int. Ed.  2006,  45:  7627 
• 11 Iwama T. Rawal VH. Org. Lett.  2006,  8:  5725