Efficient Pd(OAc)₂/Pyrimidine Catalytic System for Suzuki-Miyaura Cross-Coupling Reaction

Abstract

A combination of Pd(OAc)₂ and 2-aminopyrimidine-4,6-diol was found to be a stable and efficient catalytic system for the Suzuki-Miyaura cross-coupling of aryl halides with arylboronic acids. In the presence of Pd(OAc)₂ and 2-aminopyrimidine-4,6-­diol, various ArX (X = I, Br, and Cl) were coupled with arylboronic acids efficiently to afford the corresponding cross-coupled products in moderate to excellent yields. Furthermore, high turnover numbers (up to 1000000 for the reaction of iodobenzene with phenyl­boronic acid) for the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction were observed.

Key words

Pd(OAc)₂ - pyrimidine - aryl halide - Suzuki-Miyaura cross-coupling reaction - arylboronic acid

References

• 1a Bringmann G. Walter R. Weirich R. Angew. Chem., Int. Ed. Engl.  1990,  29:  977 
• 1b Hegedus LS. In Organometallics in Synthesis   Schlosser MJ. Wiley & Sons; Chichester: 2002.  p.1123 
• 1c Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley-Interscience; New York: 2002. 
• For reviews, see:
• 2a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 2b Diederich F. Stang PJ. Metal-Catalyzed Cross-Coupling Reactions   Wiley-VCH; Weinheim: 1998. 
• 2c Miyaura N. Cross-Coupling Reactions   Springer; Berlin: 2002. 
• 2d Nakamura I. Yamamoto Y. Chem. Rev.  2004,  104:  2127 
• 2e Bellina F. Carpita A. Rossi R. Synthesis  2004,  2419 
• For recent representative papers on phosphine-palladium catalysts, see:
• 3a Old DW. Wolfe JP. Buchwald SL. J. Am. Chem. Soc.  1998,  120:  9722 
• 3b Wolfe JP. Singer RA. Yang BH. Buchwald SL. J. Am. Chem. Soc.  1999,  121:  9550 
• 3c Littke AF. Dai C. Fu GC. J. Am. Chem. Soc.  2000,  122:  4020 
• 3d Bedford RB. Cazin CSJ. Hazelwood SL. Angew. Chem. Int. Ed.  2002,  41:  4120 
• 3e Feuerstein M. Berthiol F. Doucet H. Santelli M. Synlett  2002,  1807 
• 3f Mori K. Yamaguchi K. Hara T. Mizugaki T. Ebitani K. Kaneda K. J. Am. Chem. Soc.  2002,  124:  11572 
• 3g Yin J. Rainka MP. Zhang X.-X. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  1162 
• 3h Littke AF. Schwarz L. Fu GC. J. Am. Chem. Soc.  2002,  124:  6343 
• 3i Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
• 3j Kwong FY. Lam WH. Yeung CH. Chan KS. Chan ASC. Chem. Commun.  2004,  2336 
• 3k Brenstrum T. Gerristma DA. Adjabeng GM. Frampton CS. Britten J. Robertson AJ. McNulty J. Capretta A. J. Org. Chem.  2004,  69:  77635 
• 3l Baillie C. Zhang L. Xiao J. J. Org. Chem.  2004,  69:  7779 
• 3m DeVasher RB. Moore LR. Shaughnessy KH. J. Org. Chem.  2004,  69:  7919 
• 3n Mukherjee A. Sarkar A. Tetrahedron Lett.  2004,  45:  9525 
• 3o Zhang W. Shi M. Tetrahedron Lett.  2004,  45:  8921 
• 3p Peyroux E. Berthiol F. Doucet H. Santelli M. Eur. J. Org. Chem.  2004,  1075 
• 3q Willis MC. Powell LH. Claverie CK. Angew. Chem. Int. Ed.  2004,  43:  1249 
• 3r Wang A.-E. Zhang J. Xie J.-H. Li K. Zhou Q.-L. Adv. Synth. Catal.  2004,  346:  595 
• 3s Berthiol F. Kondolff I. Doucet H. Santelli M. J. Organomet. Chem.  2004,  689:  2786 
• 3t Okamoto K. Akiyama R. Kobayashi S. Org. Lett.  2004,  6:  1987 
• 3u Barder TE. Buchwald SL. Org. Lett.  2004,  6:  2649 
• 3v Colacot TJ. Shea HA. Org. Lett.  2004,  6:  3731 
• For recent reviews on N-heterocyclic carbene-palladium catalysts, see:
• 4a Herrmann WA. Angew. Chem. Int. Ed.  2002,  41:  1290 
• 4b Yong BS. Nolan SP. Chemtracts: Org. Chem.  2003,  205 
• 5 For a recent representative paper on thiourea-palladium catalysts, see: Dai M. Liang B. Wang C. Chen J. Yang Z. Org. Lett.  2004,  6:  221 
• For recent representative papers on diazabutadiene-palladium catalysts, see:
• 6a Grasa GA. Hillier AC. Nolan SP. Org. Lett.  2001,  3:  1077 
• 6b Palencia H. Garcia-Jimenez F. Takacs JM. Tetrahedron Lett.  2004,  45:  3849 
• For recent representative papers on amine-palladium catalysts, see:
• 7a Tao B. Boykin DW. Tetrahedron Lett.  2003,  43:  7993 
• 7b Tao B. Boykin DW. J. Org. Chem.  2004,  69:  4330 
• 7c Li J.-H. Liu W.-J. Org. Lett.  2004,  6:  2809 
• For recent representative papers on other phosphine-free-ligand-palladium catalysts, see:
• 8a Tao B. Boykin DW. Tetrahedron Lett.  2002,  43:  4955 
• 8b Alonso DA. Nájera C. Pacheco MC. Org. Lett.  2000,  2:  1823 
• 8c Botella L. Nájera C. Angew. Chem. Int. Ed.  2002,  41:  179 
• 8d Bedford RB. Cazin CS. Chem. Commun.  2001,  1540 
• 8e Alonso DA. Nájera C. Pacheco MC. J. Org. Chem.  2002,  67:  5588 ; and reference cited therein
• 8f de Vries AHM. Mulders JMCA. Mommers JHM. Henderickx HJW. de Vries JG. Org. Lett.  2003,  5:  3285 ; and references cited therein
• 8g Altenholf G. Goddard R. Lehmann CW. Glorius F. Angew. Chem. Int. Ed.  2003,  42:  3690 
• 8h Gupta AK. Rim CY. Oh CH. Synlett  2004,  2227 
• 8i Fairlamb IJS. Kapdi AR. Lee AF. Org. Lett.  2004,  6:  4435 
• 8j Bandgar BP. Bettigeri SV. Phopase J. Tetrahedron Lett.  2004,  45:  6959 
• 8k Blanco B. Mehdi A. Moreno-Mañas M. Pleixats R. Reyé C. Tetrahedron Lett.  2004,  45:  8789 
• 8l Altenholf G. Goddard R. Lehmann CW. Glorius F. J. Am. Chem. Soc.  2004,  126:  15195 
• 8m Mino T. Shirae Y. Sakamoto M. Fujita T. J. Org. Chem.  2005,  71:  2191 
• 9a Homogeneous Catalysis with Metal Phosphine Complexes   Pignolet LH. Plenum; New York: 1983. 
• 9b Parshall GW. Ittel S. Homogeneous Catalysis   J. Wiley and Sons; New York: 1992. 
• 9c Collman JP. Hegedus LS. Norton JR. Finke RG. Principles and Applications of Organotransition Metal Chemistry   University Science; Mill Vallley CA: 1987.