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學生：洪柏楷 指導教授：于淑君　博士

Synthesis and Characterization of N -Heterocyclic Carbene Palladium(II) Complexes. The Catalytic Application on Strecker Synthesis of α- Aminonitriles. 學生：洪柏楷 指導教授：于淑君　博士. 2010 / 07 / 29 Department of Chemistry & Biochemistry Chung Cheng University. Phosphine Ligand.

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學生：洪柏楷 指導教授：于淑君　博士

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  1. Synthesis and Characterization of N-Heterocyclic Carbene Palladium(II)Complexes. The Catalytic Application on Strecker Synthesis ofα-Aminonitriles 學生：洪柏楷 指導教授：于淑君　博士 2010 / 07 / 29 Department of Chemistry & Biochemistry Chung Cheng University

  2. Phosphine Ligand • Phosphines are electronically and sterically tunable. • Expensive. • Air/water sensitive and thermally unstable. • Metal leaching. • Chemical waste - water bloom. 25 mL 211.5 USD 100 mL 31.9 USD 25 G 396 USD 10G 135.5USD

  3. N-Heterocyclic Carbenes [M] • NHCs are stronger σ-donor and weaker π-acceptor than the most electron rich phosphines . • NHCs can be useful spectator ligands, because they are sterically and electronically tunable. • NHCs can promote a wide series of catalytic reactions like phosphine. • NHCs have advantages over phosphines and offer catalysts with better air- and thermal stability.

  4. N-Heterocyclic Carbenes as Ligands • In the early 90's NHC were found to have bonding properties similar to • trialklyphosphanes and alkylphosphinates. • - compatible with both high and low oxidation state metals • - examples: • - reaction employing NHC's as ligands: Herrmann, W. A.; Öfele, K; Elison, M.; Kühn, F. E.; Roesky, P. W. J. Organomet. Chem.1994, 480, C7-C9. Herrmann, W. Angew. Chem. Int. Ed.2002, 41, 1290-1309.

  5. The Catalytic Applications of Pd(II) • C-H Activation of Methane • Oxidation of Alcohols • Reductive Aldol Reaction • Allylation of Aldehydes • Strecker Reaction • Heck reaction • Suzuki–Miyaura Reaction • Carbon-Surfur Coupling Reactions • Buchwald-Hartwig Reactions • Etherification Reaction • Ethylene-CO copolymerization Reaction

  6. How does the life start on earth • Miller experiment – Water, methane, ammonia and hydrogen. Stanley L. Miller . Science 1953, 117, 528-529.

  7. Strecker AminoAcidSynthesis • The Strecker amino acid synthesis is a series of chemical reactions that synthesize an amino acid from an aldehyde (or ketone). • Adolph Strecker was the first to understand this organic reaction at 1850. • Two novel organogallium(III) complexes were tested in vitro against human tumour. Strecker, D. Ann.Chem. Pharm.1850, 75, 27-45. Santiago Gomez-Ruiz , Milena R. Journal of Organometallic Chemistry 2009, 694, 2191–2197.

  8. Lewis Acid-Catalyzed Strecker Reactions • Lewis acid catalysts • Et3N、InCl3、Ga(OTf)3、BiCl3 • Paraskar, A. S.; Sudalai, A. Tetrahedron Lett.2006, 47, 5759-5762. • Ranu, B. C.; Dey, S. S.; Hajra, A. Tetrahedron2002, 58, 2529-2532. • Surya Prakash, G. K.; Mathew, T. ; Panja, C.; Alconcel, S.; Vaghoo, H.; Do, C.; Olah, G. A. • PNAS 2007,104, 3703-3706. • De, S. K. ; Gibbs, R. A. Tetrahedron Lett.2004, 45, 7407-7408. • Transition metal Lewis acid catalysts • RuCl3、NiCl2、Sc(OTf)3、Cu(OTf)2 • De, S. K. Synth. Commun.2005, 35, 653-656. • De, S. K. J. Mol. Catal. A: Chem.2005, 225, 169-171. • Lanthanide Lewis acid catalysts • Pr(OTf)3、La(O-i-Pr)、Yb(OTf)3 • De, S. K. Synth. Commun.2005, 35, 961-966. • Others • KSF、I2 • Yadav, J. S.; Subba Reddy, B. V.; Eeshwaraiah B.; Srinivas, M. Tetrahedron 2004, 60, 1767-1771. • Royer, L.; De, S. K.; Gibbs, R. A. Tetrahedron Lett.2005, 46, 4595-4597.

  9. Motivation • Using NHCs ligand to replace phosphine ligand in • organomatallic catalysis. • Synthesis of NHC-Pd(II) complexes with well-defined structures. • Developing a practical and effective process for the • Strecker Reactions. • Greener catalysis –solventless and microwave conditions.

  10. The First Palladium(II) Carbene Complexes Toshikazu Hirao, Kenji Tsubata.Tetrahedron Letters 1978 , 18, 1535 - 1538.

  11. Examples of Pd(II)-Carbene Complexes Lijin Xu, Weiping Chen Organometallics, 2000, 19, 1123-1127 . Yuan Han, Han Vinh Huynh, Journal of Organometallic Chemistry, 2007, 692, 3606–3613.

  12. Examples of Pd(II)-Carbene Complexes Yuan Han, Han Vinh Huynh, Journal of Organometallic Chemistry, 2007, 692, 3606–3613.

  13. Synthesis of Palladium(Il) Carbene Complexes (hmim)HI hmim = 1-hexyl-3-methylimidazolium PdI2(hmim)2

  14. Synthesis of Pd(Il) Carbene Complex Catalyst Pd(hmim)2(OOCCF3)2

  15. 1H NMRSpectraof (hmim)HI (2), PdI2(hmim)2 (3), andPd(hmim)2(OOCCF3)2 (4) *CDCl3 CH3 2H H

  16. 13C NMRSpectraof (hmim)HI (2), PdI2(hmim)2 (3), andPd(hmim)2(OOCCF3)2 (4) *CDCl3 q,1J(C,F) =288.0Hz q,2J(C,F) =36.0Hz C C C

  17. 19F NMRof Pd(hmim)2(OOCCF3)2 (4) F

  18. IRSpectraof (hmim)HI (2), PdI2(hmim)2 (3), andPd(hmim)2(OOCCF3)2 (4) Pd(hmim)2(OOCCF3)2 (4) 1576 3133, 3162 2957, 2933, 2861 1868 (C=O) 1190 PdI2(hmim)2 (3) 1219 3113, 3149 1566 2954, 2928, 2857 imidazole ν (ring stretching) (hmim)HI (2) 1166 2953,2930,2857 1569 imidazole H–C–C & H–C–N bending 3079,3140 aliphatic ν (C–H) imidazole ring ν (C–H)

  19. Single-Crystal StructureofPdI2(hmim)2 (3) dihedral angle 8.20 ° Range of Pd(II)-C 1.97 ~ 2.30 Å

  20. N-Heterocyclic Carbene Complexes of Palladium ---- cis / trans-Isomerization rt, 24 h d-CDCl3 d-CDCl3 trans-anti : trans-syn = 1:1 trans-anti : trans-syn = 5:1 Lijin Xu, Weiping Chen Organometallics, 2000, 19, 1123-1127 .

  21. PdI2(hmim)2 (3) trans-syn and trans-anti Isomerization PdI2(hmim)2 (3) recrystalized from toluene + hexane (1:15) 4.363 4.325 4.287 + 3.952 4.380 4.362 4.330 4.301 4.285 + 3.951 3.935 trans-anti trans-syn : trans-anti = 1:1 rt, 12h 200 NMR 50 °C, 12h d-CDCl3 PdI2(hmim)2(3)

  22. Strecker Reaction Jiacheng Wang, Yoichi Masui, Makoto Onaka Eur. J. Org. Chem. 2010, 1763–1771.

  23. Examples of Catalytic Strecker Reaction of Ketones Thomas Mathew, Chiradeep Panja, Steevens Alconcel.PNAS.2007,104, 3703–3706. Noor-ul H. Khan, Santosh Agrawal .Tetrahedron Letters. 2008, 49, 640–644. Jiacheng Wang, Yoichi Masui, Makoto Onaka Eur. J. Org. Chem. 2010, 1763–1771.

  24. Examples of Catalytic Strecker Reaction of Ketones Jamie Jarusiewicz, Yvonne Choe. J. Org. Chem. 2009, 74, 2873–2876. Jing Nie, Teng Wanga , Jun An Ma Org. Biomol. Chem.2010, 8, 1399–1405.

  25. Pd(II)-Catalyzed Strecker Reactions

  26. Pd(hmim)2(OOCCF3)2 (4) Catalyzed Strecker Reactions Reaction Conditions : Catalyst Loading = 3 mol % ; Benzaldehyde = 0.2 mmol; Aniline = 0.2 mmol, TMSCN = 0.4 mmol ; Sodium Sulfate = 0.7 mmol. The conversion is determined by 1H NMR.

  27. Strecker Reaction Under Catalyst-Free Conditions Reaction Conditions : Aldehyde = 0.2 mmol; Benzylamine = 0.2 mmol, TMSCN = 0.4 mmol. The conversion is determined by 1H NMR. aPdI2(hmim)2 (3) as catalyst (3 mol%).

  28. PdI2(hmim)2 (3)-Catalyzed Strecker Reactions Reaction Conditions : Catalyst Loading = 3 mol % ; Aldehyde = 0.2 mmol; Aniline = 0.2 mmol, TMSCN = 0.4 mmol. The conversion is determined by 1H NMR. aPd(hmim)2(OOCCF3)2 (4) as catalyst.

  29. PdI2(hmim)2 (3)-Catalyzed Strecker Reactions Reaction Conditions : Catalyst Loading = 3 mol % ; Benzaldehyde = 0.2 mmol; Amine = 0.2 mmol, TMSCN = 0.4 mmol. The conversion is determined by 1H NMR.

  30. Comparison of 3-Catalyzed Strecker Reactions with Reported Data Reaction Conditions : Catalyst Loading = 3 mol % ; Aldehyde = 0.2 mmol; Aniline = 0.2 mmol, TMSCN = 0.4 mmol. The conversion is determined by 1H NMR.

  31. Comparison of 3-Catalyzed Strecker Reactions with Reported Data Reaction Conditions : Catalyst Loading = 3 mol % ; Benzaldehyde = 0.2 mmol; Amine = 0.2 mmol, TMSCN = 0.4 mmol. The conversion is determined by 1H NMR.

  32. PdI2(hmim)2 (3) and Pd(hmim)2(OOCCF3)2 (4)-Catalyzed Strecker Reactions of Ketone Reaction Conditions : Catalyst Loading = 3 mol % ; Acetophenone = 0.2 mmol; Aniline = 0.2 mmol, TMSCN = 0.4 mmol . The conversion is determined by 1H NMR.

  33. Microwave-Assisted PdI2(hmim)2 (3) and Pd(hmim)2(OOCCF3)2 (4)-Catalyzed Strecker Reaction of Ketones Reaction Conditions : Catalyst Loading = 3 mol % ; Acetophenone = 0.2 mmol; Aniline = 0.2 mmol, TMSCN = 0.4 mmol . The conversion is determined by 1H NMR.

  34. Microwave-Assisted PdI2(hmim)2 (3) and Pd(hmim)2(OOCCF3)2 (4)-Catalyzed Strecker Reactions Reaction Conditions : Catalyst Loading = 3 mol % ; Ketone = 0.2 mmol; Amine = 0.2 mmol, TMSCN = 0.4 mmol; (Bmim)PF6 = 2 drops; Power = 150W. The conversion is determined by 1H NMR.

  35. PdI2(hmim)2 (3)-Catalyzed Strecker Reactions Benzyl amine (pKb= 4.67) Aniline (pKb= 9.3) Kobayashi S.; Tsuchiya Y.; Mukaiyama T. Chemistry Letters, 1991, 537-540.

  36. Comparison of 3-Catalyzed Strecker Reactions with Reported Data Reaction Conditions : Catalyst Loading = 3 mol % ; Ketone = 0.2 mmol; Amine = 0.2 mmol, TMSCN = 0.4 mmol; (Bmim)PF6 = 2 drops; Power = 150W. The conversion is determined by 1H NMR. a Ga(OTf)3,bFe(Cp)2PF6, cBINOL-derived phosphoric acid, dPdII-NHC, eSn-Mont

  37. Comparison of 4-Catalyzed Strecker Reactions with Reported Data Reaction Conditions : Catalyst Loading = 3 mol % ; Ketone = 0.2 mmol; Amine = 0.2 mmol, TMSCN = 0.4 mmol; (Bmim)PF6 = 2 drops; Power = 150W. The conversion is determined by 1H NMR. a Ga(OTf)3,bFe(Cp)2PF6, cBINOL-derived phosphoric acid, dPdII-NHC, eSn-Mont

  38. ProposedMechanism for Strecker Reaction

  39. Conclusions • We have successfully synthesized NHC-carbene Pd(II) • complexes (3) and (4), and characterized them by using 1H- • ,13C , 19F-NMR, IR spectrocopies, as well as X-ray crystallography. • We have successfully demonstrated the highly effective activity • of the Pd(II) NHC-carbene complex catalyst towards the Strecker • reactions. • Not many successful synthetic protocols for Strecker reactions • of ketones has been reported. We have demonstrated in this study • that our target Pd(II) NHC-carbene catalyst (3) and (4) is highly • active for the Strecker reactions of ketones under microwave • irradiation conditions.

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