Ligand Effects in Nickel Catalysis. Anthony S. Grillo Chem 535 Seminar October 22, 2012

Transcription

1 Ligand in Nickel Catalysis Anthony S. Grillo Chem 535 Seminar October 22, 2012

2 Transition Metals in Chemistry Organotransition Metal Chemistry, Hartwig, J. F. University Science Books: Mill Valley, CA, 2010.

3 Number of Publications The Emergence of Nickel Publication Year

4 Advanced Inorganic Chemistry, Cotton, F.A.; Wilkinson, G.; Murillo, C.A.; Bochmann, M., John Wiley and Sons, Inc.: New York, Modern Organonickel Chemistry Tamaru, Y. Wiley-VCH: Weinheim, Germany, Crystal Field Theory Ni II most commonly square planar Tetrahedral with bulky ligands (PR 3 )

5 Nickel-Catalyzed Processes Hydrogenation Hibino, T.; Makino, K.; Sugiyama, T.; Hamada, Y. Chem. Cat. Chem. 2009, 1, Hydrocyanation/amination/arylation Robbins, D. W.; Hartwig, J. F. Science 2011, 333, Multi-Component Reactions Ogata, K.; Atsuumi, Y.; Shimada, D.; Fukuzawa, S. Angew. Chem. Int. Ed. 2011, 50,

6 Nickel-Catalyzed Processes Nozaki-Hiyama-Kishi (NHK) Reaction Kobayashi, K.; Fujii, Y.; Hayakawa, I.; Kigoshi, H. Org. Lett. 2011, 13, Cycloadditions Nishimura, A.; Ohashi, M.; Ogoshi, S. J. Am. Chem. Soc. 2012, 134, Cycloisomerizations Phillips, J. H.; Montgomery, J. Org. Lett. 2010, 12,

7 Nickel-Catalyzed Processes Reductive Couplings Shareef, A.-R.; Sherman, D. H.; Montgomery, J. Chem. Sci. 2012, 3, sp 3 Cross-Couplings Huang, C.-Y.; Doyle, A. G. J. Am. Chem. Soc. 2012, 134,

8 Outline Steric Nickel Catalysis Electronic Chelation

9 Electronic Steric Nickel Catalysis Electronic Chelation

10 Electronic - Phosphines Tolman, C. A. Chem. Rev. 1997, 77,

11 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,

12 Electronic π-systems Dewar, M. Bull. Soc. Chim. Fr. 1951, 18, C79. Chatt, J.; Duncanson, L. A. J. Chem. Soc. 1953, Vicic, D. A. et al. J. Am. Chem. Soc. 2006, 128,

13 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,

14 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, Giovannini, R.; Studemann, T.; Devasagayaraj, A.; Dussin, G.; Knochel, P. J. Org. Chem. 1999, 64,

15 sp 3 Cross-Coupling Nielsen, D. K.; Doyle, A. G. Angew. Chem. Int. Ed. 2011, 50,

16 sp 3 Cross-Coupling Vicic, D. A. et al. J. Am. Chem. Soc. 2006, 128,

17 Reductive Coupling of Alkynes Miller, K. M.; Huang, W. -S.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125, Montgomery, J.; Sormunen, G. J. Top. Curr. Chem. 2007, 279, Sa-ei, K.; Montgomery, J. Org. Lett. 2006, 8, 4441.

18 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, Miller, K. M.; Huang, W. -S.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125,

19 Steric Steric Nickel Catalysis Electronic Chelation

20 Steric d 10 Ni 0 14e - Linear Species Tolman, C. A. Chem. Rev. 1997, 77, Clavier, H.; Nolan, S. P. Chem. Commun. 2010, 46, Matsubara, K.; Miyazaki, S.; Koga, Y.; Nibu, Y.; Hashimura, T.; Matsumoto, T. Organometallics, 2008, 27,

21 Reductive Ynal Couplings Malik, H. A.; Chaulagain, M. R.; Montgomery, J. Org. Lett. 2009, 11, Malik, H. A.; Sormunen, G. J.; Montgomery, J. J. Am. Chem. Soc. 2010, 132,

22 Reductive Ynal Couplings Liu, P.; Montgomery, J.; Houk, K. N. J. Am. Chem. Soc. 2011, 133,

23 Reductive Ynal Couplings Shareef, A.-R.; Sherman, D. H.; Montgomery, J. Chem. Sci. 2012, 3,

24 Chelation Steric Nickel Catalysis Electronic Chelation

25 Chelation Zhou, J.; Fu, G. C. J. Am. Chem. Soc. 2003, 125, Fischer, C.; Fu, G. C. J. Am. Chem. Soc. 2005, 127,

26 Chelation Red. Elimination Bite Angle Dierkes, P.; van Leeuwen, P. W. N. M. J. Chem. Soc., Dalton Trans., 1999,

27 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,

28 sp 3 Cross-Coupling Vechorkin, O.; Hu, X. L. Angew. Chem., Int. Ed. 2009, 48, Binder, J. T.; Cordier, C. J.; Fu, G. C. J. Am. Chem. Soc. 2012, 134,

29 Summary

30 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

31 1 vs. 2 electron

32 Sq. Planar vs. Tetrahedral Modern Organonickel Chemistry Tamaru, Y. Wiley-VCH: Weinheim, Germany, 2005.

33 Electronic Steric Nickel Catalysis Electronic Chelation

34 Steric Steric Nickel Catalysis Electronic Chelation

35 Chelation Steric Nickel Catalysis Electronic Chelation

36 Nickel Catalysis Steric Nickel Catalysis Electronic Chelation

37 Acknowledgements Professor Burke Professor Hergenrother Chem 535 Burke Group