Neue metallorganische Funktionalisierung von Heterozyklen

• Applicant: Professor Dr. Paul Knochel
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2006 to 2011
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 33545288

• Final Report Year: 2011

Final Report Abstract

Wir haben eine Reihe neuer synthetischer Methoden entwickelt, die metallorganische Intermediate verwenden. Diese Methoden erlauben es, eine breite Palette von heterozyklischen Verbindungen zu synthetisieren. Diese Arbeiten haben eine große Resonanz bei der Pharma-Industrie gefunden: aktuelle (2011) Kooperationen finden zurzeit in unseren Laboratorien statt, welche auf Arbeiten basieren, die in diesem Bericht beschrieben sind.

Publications

• Efficient Synthesis of Functionalized Organozinc Compounds by the Direct Insertion of Zinc into Organic Iodides and Bromides. Angewandte Chemie International Edition, Vol. 45. 2006, Issue 36, pp. 6040–6044.
  Krasovskiy, A.; Malakhov, V.; Gavryushin, A.; Knochel, P.
  (See online at https://dx.doi.org/10.1002/anie.200601450)
• Selective Functionalization of Imidazoles via an Iodine-Copper Exchange Reaction. Chemical Communications, Vol. 20. 2006, pp. 2170-2172.
  Yang, X.; Knochel, P.
  (See online at https://dx.doi.org/10.1039/B603419E)
• Direct Aminoalkylation of Arenes and Hetarenes via Ni- Catalyzed Negishi Cross-Coupling Reactions. Organic Letters, Vol. 9. 2007, Issue 26, pp. 5529–5532.
  Melzig, L.; Gavryushin, A.; Knochel, P.
  (See online at https://dx.doi.org/10.1021/ol702499h)
• Directed Ortho Insertion (DoI): A New Approach to Functionalized Aryl and Heteroaryl Zinc Reagents. Journal of the American Chemical Society, Vol. 129. 2007, Issue 41, pp. 12358-12359.
  Boudet, N.; Sase, S.; Sinha, P.; Liu, C.-Y.; Krasovskiy, A.; Knochel, P.
  (See online at https://dx.doi.org/10.1021/ja074060h)
• Multiple Regioselective Functionalizations of Quinolines via Magnesiations. Organic Letters, Vol. 9. 2007, Issue 26, pp. 5525-5528.
  Boudet, N.; Lachs, J. R.; Knochel, P.
  (See online at https://dx.doi.org/10.1021/ol702494k)
• An Efficient Silane-Promoted Nickel-Catalyzed Amination of Aryl and Heteroaryl Chlorides. Journal of Organic Chemistry, Vol. 73. 2008, Issue 4, pp. 1429-1434.
  Manolikakes, G.; Gavryushin, A.; Knochel, P.
  (See online at https://dx.doi.org/10.1021/jo702219f)
• High Temperature Metalation of Functionalized Aromatics and Heteroaromatics using (tmp)2Zn·2MgCl2 2LiCl and Microwave Irradiation. Organic Letters, Vol. 10. 2008, Issue 20, pp. 4705-4707.
  Wunderlich, S.; Knochel, P.
  (See online at https://dx.doi.org/10.1021/ol802118e)
• Multiple Regio- and Chemoselective Functionalizations of Pyrimidine Derivatives Using TMPMgCl·LiCl and TMP2Mg·2LiCl. Synthesis, Vol. 22. 2008, pp. 3697-3702.
  Mosrin, M.; Petrera, M.; Knochel, P.
  (See online at https://dx.doi.org/10.1055/s-0028-1083208)
• Polyfunctionalizations of N-Heterocycles via Chemo- and Regioselective Metalations, Dissertation, Fakultät für Chemie und Pharmazie der Ludwig-Maximilians-Universität München, 2008.
  Nadège Boudet
  
• 2,3-Functionalization of Furans, Benzofurans and Thiophenes via Magnesiation and Sulfoxide-Magnesium Exchange. Chemical Communications, Vol. 24. 2009, pp. 3536-3538.
  Melzig, L.; Rauhut, C B.; Knochel, P.
  (See online at https://dx.doi.org/10.1039/b907330b)
• Br/Mg-Exchange on 1,2-Dibromocyclopentene Derivatives and Regioand Chemoselective Functionalizations of Pyrazoles and Related Heterocycles. Dissertation, LMU, Fakultät für Chemie und Pharmazie, München 2009.
  Christina Despotopoulou
  
• Directed Manganation of Functionalized Arenes and Heterocycles Using tmp2Mn·2MgCl2·4LiCl. Angewandte Chemie International Edition, Vol. 48. 2009, Issue 39, pp. 7256–7260.
  Wunderlich, S. H.; Kienle, M.; Knochel, P.
  (See online at https://dx.doi.org/10.1002/anie.200903505)
• Functionalization of 4,5-Dihydrobenzo[g]indazoles Using Magnesium- or Zinc-Heterocyclic Intermediates. Synthesis, Vol. 21.2009, pp. 3661-3671.
  Despotopoulou, C.; Gignoux, C.; McConnell, D.; Knochel, P.
  (See online at https://dx.doi.org/10.1055/s-0029-1217008)
• High Temperature Zincation of Functionalized Aromatics and Heteroaromatics Using TMPZnCl.LiCl and Microwave Irradiation. Chemical Communications, Issue 37. 2009, pp. 5615-5617.
  Mosrin, M.; Monzon, G.; Bresser, T.; Knochel, P.
  (See online at https://dx.doi.org/10.1039/b913693b)
• New Mixed Li/Mg and Li/Mg/Zn Amides for the Chemoselective Metalation of Arenes and Heteroarenes. European Journal of Organic Chemistry, Special Issue: Dedicated to Professor Alain Krief, Vol. 2009, Issue 11, pp. 1781–1795.
  Rohbogner, C. J.; Wunderlich, S. H.; Clososki, G. C.; Knochel, P.
  (See online at https://dx.doi.org/10.1002/ejoc.200801277)
• Atom-Economical Preparation of Aryl- and Heteroaryl-Lanthanum Reagents by Directed ortho-Metalation by Using tmp3[La]. Chemistry - A European Journal, Vol. 16. 2010, Issue 11, pp. 3304–3307.
  Wunderlich, S. H.; Knochel, P.
  (See online at https://dx.doi.org/10.1002/chem.200903157)
• Fischer Indole Synthesis with Organozinc Reagents. Angewandte Chemie International Edition, Vol. 49. 2010, Issue 49, pp. 9513–9516.
  Haag, B. A.; Zhang, Z.-G.; Li, J.-S.; Knochel, P.
  (See online at https://dx.doi.org/10.1002/anie.201005319)
• Phosphorodiamidate-Directed Metalation of NHeterocycles using Mg- and Zn-TMP Bases. Organic Letters, Vol. 12. 2010, Issue 9, pp. 1984–1987
  Rohbogner, C. J.; Wirth, S.; Knochel,
  (See online at https://dx.doi.org/10.1021/ol100453x)
• Regio- and Chemoselective Zincation of Sensitive and Moderately Activated Aromatics and Heteroaromatics Using TMPZnCl·LiCl. Journal of Organic Chemistry, Vol. 75.2010, Issue 14, pp. 4686–4695.
  Bresser, T.; Mosrin, M.; Monzon, G.; Knochel, P.
  (See online at https://dx.doi.org/10.1021/jo100884u)
• TMP2Mg·2LiCl and Related Bases for the Metalation of Unsaturated Substrates and the Role of the Phosphorodiamidate Directing Group. A new Cobalt-Catalyzed Sulfonate/Copper-Exchange. Dissertation, LMU München: Fakultät für Chemie und Pharmazie, 2010.
  Christoph Rohbogner