A Rationally Designed Universal Catalyst for Suzuki–Miyaura Coupling Processes

Angewandte Chemie International EditionVolume 43, Issue 14 p. 1871-1876 Communication A Rationally Designed Universal Catalyst for Suzuki–Miyaura Coupling Processes† Shawn D. Walker Dr., Shawn D. Walker Dr. Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this authorTimothy E. Barder, Timothy E. Barder Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this authorJoseph R. Martinelli, Joseph R. Martinelli Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this authorStephen L. Buchwald Prof. Dr., Stephen L. Buchwald Prof. Dr. [email protected] Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this author Shawn D. Walker Dr., Shawn D. Walker Dr. Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this authorTimothy E. Barder, Timothy E. Barder Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this authorJoseph R. Martinelli, Joseph R. Martinelli Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this authorStephen L. Buchwald Prof. Dr., Stephen L. Buchwald Prof. Dr. [email protected] Department of Chemistry, Room 18-490, Massachusetts Institute of Technology, Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297Search for more papers by this author First published: 24 March 2004 https://doi.org/10.1002/anie.200353615Citations: 806 † We thank the National Institutes of Health (GM 46059) for support of this work. We are grateful to Merck, Pfizer, Rhodia, Lundbeck, and Novartis for additional support. T.E.B. would like to thank Dr. W. M. Davis for assistance with the X-ray crystal structure. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Unprecedented scope, reactivity, and stability are displayed by a new catalyst system. This was demonstrated with general and efficient syntheses of sterically hindered (hetero)biaryls (see examples shown), mild coupling reactions of alkyl boron derivatives, and rapid coupling reactions of aryl chlorides at room temperature. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2004/z53615_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1Recent reviews: 1aN. Miyaura, Top. Curr. Chem. 2002, 219, 11; 1bJ. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 2002, 102, 1359; 1cS. Kotha, K. Lahiri, D. Kashinath, Tetrahedron 2002, 58, 9633. 2The majority of the examples demonstrating high turnover numbers for the coupling reactions of unactivated substrates use phenyl boronic acid as the coupling partner. However, success with this substrate rarely translates into similiar levels of activity or generality with even slightly more hindered or functionalized substrates. For recent examples of cross-couplings employing phenyl boronic acid see: 2aA. Zapf, R. Jackstell, F. Rataboul, T. Riermeier, A. Monsees, C. Fuhrmann, N. Shaikh, U. Dingerdissen, M. Beller, Chem. Commun. 2004, 1, 38; 2bN. Leadbeater, M. Marco, Angew. Chem. 2003, 115, 1445; Angew. Chem. Int. Ed. 2003, 42, 1407; 2cR. B. Bedford, C. S. J. Cazin, S. J. Coles, T. Gelbrich, P. N. Horton, M. B. Hursthouse, M. E. Light, Organometallics 2003, 22, 987; 2dJ. P. Stambuli, R. Kuwano, J. F. Hartwig, Angew. Chem. 2002, 114, 940; Angew. Chem. Int. Ed. 2002, 41, 4746; 2eA. Zapf, A. Ehrentraut, M. Beller, Angew. Chem. 2000, 112, 4315; Angew. Chem. Int. Ed. 2000, 39, 4153. 3 3aS. Kaye, J. M. Fox, F. A. Hicks, S. L. Buchwald, Adv. Synth. Catal. 2001, 343, 789; 3bH. Tomori, J. M. Fox, S. L. Buchwald, J. Org. Chem. 2000, 65, 5334. 4E. R. Strieter, D. G. Blackmond, S. L. Buchwald, J. Am. Chem. Soc. 2003, 125, 13 978. 5For a review see: A. D. Ryabov, Chem. Rev. 1990, 90, 403. 6 6aJ. Yin, M. P. Rainka, X.-X. Zhang, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 1162; 6bS. M. Reid, R. C. Boyle, J. T. Mague, M. J. Fink, J. Am. Chem. Soc. 2003, 125, 7816; 6cT. E. Barder, X.-X. Zhang, S. L. Buchwald, unpublished results. 7 7aJ. P. Wolfe, R. A. Singer, B. H. Yang, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 9550; 7bR. B. Bedford, S. L. Hazelwood, M. E. Limmert, Chem. Commun. 2002, 2610. The presence of underligated Pd complexes may promote the formation of Pd black. For a recent study on the deactivation processes of homogeneous Pd catalysts see: M. Tromp, J. R. A. Sietsma, J. A. van Bokhoven, G. P. F. van Strijdonck, R. J. van Haaren, A. M. J. van der Eerden, P. W. N. M. van Leeuwen, D. C. Koningsberger, Chem. Commun. 2003, 128. 8For a review on Pd-catalyzed couplings of aryl chlorides see: A. F. Littke, G. C. Fu, Angew. Chem. 2002, 114, 4350; Angew. Chem. Int. Ed. 2002, 41, 4176. 9 9aA. F. Littke, C. Dai, G. C. Fu, J. Am. Chem. Soc. 2000, 122, 4020; 9bS.-Y. Liu, M. J. Choi, G. C. Fu, Chem. Commun. 2001, 2408; 9cG. Altenhoff, R. Goddard, C. W. Lehmann, F. Glorius, Angew. Chem. 2003, 115, 3818; Angew. Chem. Int. Ed. 2003, 42, 3690; 9dO. Navarro, R. A. Kelly III, S. P. Nolan, J. Am. Chem. Soc. 2003, 125, 16 194; 9eThe best previous results for this reaction are described in ref. [2c], although no yield of isolated product is reported. 10The half-life was determined by GC analysis. 11While exceedingly high turnover numbers have been realized for the coupling of phenyl boronic acid with 4-bromoacetophenone, this is a particularly trivial process and does not extend to the efficient coupling of unactivated and ortho-substituted substrates at low catalyst levels. We have previously shown this reaction to proceed even in the absence of added ligand and recommend that it not be used as a benchmark to test new catalysts, see ref. [7a]. 12For a recent report describing the cross-coupling of aryl chlorides with alkyl boronic acids, see: N. Kataoka, Q. Shelby, J. P. Stambuli, J. F. Hartwig, J. Org. Chem. 2002, 67, 5553. For a report describing the coupling of an alkyl boronic acid with an alkyl bromide, see: J. H. Kirchhoff, M. R. Netherton, I. D. Hills, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 13 662. 13Crystals suitable for X-ray diffraction were obtained by stirring a solution of [Pd2(dba)3] and 1 in benzene for 5 d, concentrating the resulting mixture, and inducing crystallization by slow evaporation from hexane (in a glovebox). Crystal data for 5: C41H49O3PPd, crystals from hexane, Mr=727.17, 0.20×0.18×0.14 mm3, triclinic, space group P (No. 2), a=11.4552(15), b=11.6697(15), c=15.5298(19) Å, α=94.058(2), β=96.084(2), γ=114.705(2)°, V=1860.1(4) Å3, Z=2, ρcalcd=1.298 g cm−3, T=193(2) K, F(000)=760, 2θmax=46.58°, monochromated MoKα radiation, λ=0.71073 Å, μ=0.577 mm−1, Siemens Platform three-circle diffractometer equipped with a CCD detector, 7703 measured and 5293 independent reflections, Rint=0.0200, 4858 reflections with I>2σ(I). Data processed using the program SAINT supplied by Siemens Industrial Automation, Inc., structure determination by direct methods (SHELXTL V6.10, G. M. Sheldrick, University of Göttingen, and Siemens Industrial Automation, Inc.), structure refined on F2 by full-matrix least-squares methods, absorption correction applied with SADABS. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were located in the electron density map and refined isotropically. The refinement of 435 parameters using 5293 reflections and 0 restraints gave R1=0.0286, wR2=0.0676 (I>2σ(I) data), goodness of fit on F2=1.052, Δρmax/min=0.509/−0.338 e Å−3. CCDC-227390 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or [email protected]). 14 14aP. Kocovsky, S. Vyskocil, I. Cisarova, J. Sejbal, I. Tislerova, M. Smrcina, G. C. Lloyd-Jones, S. C. Stephen, C. P. Butts, M. Murray, V. Langer, J. Am. Chem. Soc. 1999, 121, 7714; 14bT. Hayashi, H. Iwamura, M. Naito, Y. Matsumoto, Y. Uozumi, M. Miki, K. Yanagi, J. Am. Chem. Soc. 1994, 116; 775; 14cP. Dotta, P. G. A. Kumar, P. S. Pregosin, A. Albinati, S. Rizzato, Organometallics 2003, 22, 5345. 15T. E. Barder, S. L. Buchwald, unpublished results. 16Enhanced activity in CN bond-forming processes with a related ligand have been attributed to the formation of a PdII palladate species.[14a] While we cannot unequivocally rule this out, the fact that higher levels of catalytic activity for analogous C–N couplings have been observed for catalysts derived from 2-dicyclohexylphosphanyl-2′,4′,6′-triisopropylbiphenyl than for 1 (E. R. Strieter, S. L. Buchwald, unpublished results) cast doubt on this explanation of the high level of catalytic activity manifested with 1. Citing Literature Volume43, Issue14March 26, 2004Pages 1871-1876 ReferencesRelatedInformation