Ligand in Nickel Catalysis Anthony S. Grillo Chem 535 Seminar October 22, 2012
Transition Metals in Chemistry Organotransition Metal Chemistry, Hartwig, J. F. University Science Books: Mill Valley, CA, 2010.
Number of Publications The Emergence of Nickel 8000 6000 4000 2000 0 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 Publication Year www.scifinder.cas.org www.sigmaaldrich.com
Advanced Inorganic Chemistry, Cotton, F.A.; Wilkinson, G.; Murillo, C.A.; Bochmann, M., John Wiley and Sons, Inc.: New York, 1999. Modern Organonickel Chemistry Tamaru, Y. Wiley-VCH: Weinheim, Germany, 2005. Crystal Field Theory Ni II most commonly square planar Tetrahedral with bulky ligands (PR 3 )
Nickel-Catalyzed Processes Hydrogenation Hibino, T.; Makino, K.; Sugiyama, T.; Hamada, Y. Chem. Cat. Chem. 2009, 1, 237-240. Hydrocyanation/amination/arylation Robbins, D. W.; Hartwig, J. F. Science 2011, 333, 1423-1427. Multi-Component Reactions Ogata, K.; Atsuumi, Y.; Shimada, D.; Fukuzawa, S. Angew. Chem. Int. Ed. 2011, 50, 5896-5899.
Nickel-Catalyzed Processes Nozaki-Hiyama-Kishi (NHK) Reaction Kobayashi, K.; Fujii, Y.; Hayakawa, I.; Kigoshi, H. Org. Lett. 2011, 13, 900-903. Cycloadditions Nishimura, A.; Ohashi, M.; Ogoshi, S. J. Am. Chem. Soc. 2012, 134, 15692-15695. Cycloisomerizations Phillips, J. H.; Montgomery, J. Org. Lett. 2010, 12, 4556-4559.
Nickel-Catalyzed Processes Reductive Couplings Shareef, A.-R.; Sherman, D. H.; Montgomery, J. Chem. Sci. 2012, 3, 892-895. sp 3 Cross-Couplings Huang, C.-Y.; Doyle, A. G. J. Am. Chem. Soc. 2012, 134, 9541-9544.
Outline Steric Nickel Catalysis Electronic Chelation
Electronic Steric Nickel Catalysis Electronic Chelation
Electronic - Phosphines Tolman, C. A. Chem. Rev. 1997, 77, 313-348.
Electronic NHCs Dorta, R.; Stevens, E. D.; Scott, N. M.; Costabile, C.; Cavallo, L.; Hoff, C. D.; Nolan, S. P. J. Am. Chem. Soc. 2005, 127, 2485-2495.
Electronic π-systems Dewar, M. Bull. Soc. Chim. Fr. 1951, 18, C79. Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, 2939. Vicic, D. A. et al. J. Am. Chem. Soc. 2006, 128, 13175-13183.
sp 3 Cross-Coupling Sp 3 cross-coupling is difficult Slow oxidative addition Sterics, electronics Prone to isomerization through β-hydride Elimination Metal-alkyl complexes are generally not stabilized M = Pd, Ni, Fe, Co, etc. X = I, Br, Cl, F, S, OR, NR 2, SR, etc. M = B, Sn, Zn, Mg, Zr, Si, X, etc. R = Ar, Alkyl, Alkynyl, B, N, etc. Slow transmetalation Rudolph, A.; Lautens, M. Angew. Chem. Int. Ed. 2009, 48, 2656-2670.
sp 3 Cross-Coupling Olefin necessary Binding as π-acid decreases rate of β-hydride Elimination Makes nickel more electrophilic for transmetalation Devasagayaraj, A.; Studemann, T.; Knochel, P. Angew. Chem., Int. Ed. 1995, 34, 2723-2725. Giovannini, R.; Studemann, T.; Devasagayaraj, A.; Dussin, G.; Knochel, P. J. Org. Chem. 1999, 64, 3544-3553.
sp 3 Cross-Coupling Nielsen, D. K.; Doyle, A. G. Angew. Chem. Int. Ed. 2011, 50, 6056-6059.
sp 3 Cross-Coupling Vicic, D. A. et al. J. Am. Chem. Soc. 2006, 128, 13175-13183.
Reductive Coupling of Alkynes Miller, K. M.; Huang, W. -S.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125, 3442-3443. Montgomery, J.; Sormunen, G. J. Top. Curr. Chem. 2007, 279, 1-23. Sa-ei, K.; Montgomery, J. Org. Lett. 2006, 8, 4441.
Reductive Coupling of Alkynes Evidence Isotope Labeling Kinetics Stoichiometric Studies IR X-Ray Analysis Proposed TS Baxter, R. D.; Montgomery, J. J. Am. Chem. Soc. 2011, 133, 5728-5731. Miller, K. M.; Huang, W. -S.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125, 3442-3443.
Steric Steric Nickel Catalysis Electronic Chelation
Steric d 10 Ni 0 14e - Linear Species Tolman, C. A. Chem. Rev. 1997, 77, 313-348. Clavier, H.; Nolan, S. P. Chem. Commun. 2010, 46, 841-861. Matsubara, K.; Miyazaki, S.; Koga, Y.; Nibu, Y.; Hashimura, T.; Matsumoto, T. Organometallics, 2008, 27, 6020-6024.
Reductive Ynal Couplings Malik, H. A.; Chaulagain, M. R.; Montgomery, J. Org. Lett. 2009, 11, 5734-5737. Malik, H. A.; Sormunen, G. J.; Montgomery, J. J. Am. Chem. Soc. 2010, 132, 6304-6305.
Reductive Ynal Couplings Liu, P.; Montgomery, J.; Houk, K. N. J. Am. Chem. Soc. 2011, 133, 6956-6959.
Reductive Ynal Couplings Shareef, A.-R.; Sherman, D. H.; Montgomery, J. Chem. Sci. 2012, 3, 892-895.
Chelation Steric Nickel Catalysis Electronic Chelation
Chelation Zhou, J.; Fu, G. C. J. Am. Chem. Soc. 2003, 125, 14726-14727. Fischer, C.; Fu, G. C. J. Am. Chem. Soc. 2005, 127, 4594-4595.
Chelation Red. Elimination Bite Angle Dierkes, P.; van Leeuwen, P. W. N. M. J. Chem. Soc., Dalton Trans., 1999, 1519-1530.
Chelation - β-h Elimination Pentacoordinate nickel decreases rate of β-h elimination Coordinatively saturated (no agostic interactions) More stabilized Ni II center Electrophilic Ni II center Other Ligands Hu, X. Chem. Sci. 2011, 2, 1867-1886.
sp 3 Cross-Coupling Vechorkin, O.; Hu, X. L. Angew. Chem., Int. Ed. 2009, 48, 2937-2940. Binder, J. T.; Cordier, C. J.; Fu, G. C. J. Am. Chem. Soc. 2012, 134, 17003-17006.
Summary
Summary Advantages Low costs relative to other transition metals Diverse range of unique reactivities Stereoconvergency and asymmetric advancements The reactivity and regioselectivity are sensitive to ligand environment Disadvantages Predictability, substrate scope, and generality are currently low Small changes in substrate, conditions, catalyst have large effects on the efficiency of catalysis for each reaction class Future Directions Production of more robust catalytic systems and precatalysts Development of general reactivity rules/trends Advancements to include carbon-heteroatom bond formation Expand applications to include tertiary alkyl halides 2-electron vs. 1-electron chemistry Square planar vs. tetrahedral chemistry
1 vs. 2 electron
Sq. Planar vs. Tetrahedral Modern Organonickel Chemistry Tamaru, Y. Wiley-VCH: Weinheim, Germany, 2005.
Electronic Steric Nickel Catalysis Electronic Chelation
Steric Steric Nickel Catalysis Electronic Chelation
Chelation Steric Nickel Catalysis Electronic Chelation
Nickel Catalysis Steric Nickel Catalysis Electronic Chelation
Acknowledgements Professor Burke Professor Hergenrother Chem 535 Burke Group