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Coordination Chemistry and Asymmetric Homogeneous Catalysis

Research in our group is primarily directed toward the coordination chemistry of main group element in unusual oxidation states, the design of novel “frustrated Lewis pairs” and applications thereof to homogeneous catalysis and organic synthesis.

Manuel Alcarazo

Dr. Manuel Alcarazo

Vita Awards Publications Lectures Official Functions
since 2008
Independent Junior Group Leader at the Max-Planck-Institut für Kohlenforschung
2005-2008
Postdoctoral research at the Max-Planck-Institut für Kohlenforschung (Prof. Dr. Alois Fürstner) on the “Design and applications of ylidic and bis-ylidic systems” and “Enantioselective protecting group-free total synthesis of ecklonialactone A and B”
2005
PhD from the Instituto de Investigaciones Químicas (CSIC) (Dr. José M. Lassaletta) on the “Synthesis and structure of new NHC-ligands”
2002
Master Degree from the University of Seville, Spain (Prof. Dr. Rosario Fernández) on the “Synthesis and applications of bis-hydrazones as ligands in asymmetric catalysis”
2000
Chemistry Degree from the University of Seville, Spain
1978
born in Alcalá de Guadaira, Spain
2011
European Research Council Starting Grant for his research “Acitivation of small molecules by organic frustrated Lewis pairs"
2011
Sigma-Aldrich-RSEQ Prize for Outstanding Emerging Researcher
2010
Thieme Journal Award 2010
2009
Young Scientist Award from the Academy of Sciences of Seville, Spain
2007
Best PhD Thesis in Chemistry, University of Seville, Spain
2005-2007
Post-Doctoral Fellowship of the Spanish Ministry of Education and Science
2005
Research Fellowship from the Spanish Council for Scientific Research (CSIC)
2001-2005
PhD Scholarship from the Spanish Ministry of Education and Science (Short stays at Aarhus, Denmark (Prof. K. A. Jørgensen) and Oxford, United Kingdom (Prof. J. M. Brown))
2001
Scholarship from the Spanish Agency of International Cooperation (Universidad Nacional Autónoma de México)
2000
Graduation Prize from the University of Seville, Spain
2000
Cooperation Scholarship with the Department of Organic Chemistry, University of Seville, Spain

Total Synthesis (I), TU Dortmund, WS 2009/2010

Principles in Organometallic Chemistry, TU Dortmund, SS 2010

Stereoselective Synthesis (I), TU Dortmund, WS 2010/2011

Stereoselective Synthesis (II), TU Dortmund, SS 2011

Total Synthesis (I), TU Dortmund, WS 2011/2012

Stereoselective Synthesis, Heinrich-Heine University Düsseldorf, SS 2012 (please find the slides here)
since 2009
Member of Global Young Faculty
since 2008
Group leader at the Max-Planck-Institut für Kohlenforschung
2012

   35. "Synthesis and reactivity of electron poor allenes: formation of completely organic frustrated Lewis pairs" D. Palomas, B. Inés, S. Holle, R. Goddard, M. Alcarazo, Dalton Trans. 2012, DOI: 10.1039/C2DT30195D.

   34. "Fullerenes as neutral carbon-based Lewis acids" J. Iglesias-Sigüenza, M. Alcarazo, Angew. Chem. 2012, 124, 1553; Angew. Chem. Int. Ed. 2012, 51, 1523.

2011

    33. "Synthesis, structure, and reactivity of carbene-stabilized phosphorus(III)-centered trications [L3P]3+" J. Petuškova, M. Patil, S. Holle, C. W. Lehmann, W. Thiel, M. Alcarazo, J. Am. Chem. Soc. 2011, 133, 20758.

    32. "Catalysis-based and protecting-group-free total syntheses of the marine oxylipins hybridalactone and the ecklonialactones A, B, and C" V. Hickmann, A. Kondoh, B. Gabor, M. Alcarazo, A. Fürstner, J. Am. Chem. Soc. 2011, 133, 13471.

    31. "Synthesis, structure, and reactivity of a dihydrido borenium cation" B. Inés, M. Patil, J. Carreras, R. Goddard, W. Thiel, M. Alcarazo, Angew. Chem. 2011, 123, 8550; Angew. Chem. Int. Ed. 2011, 50, 8400.

    30. "Cyclopropenylylidene-stabilized diaryl and dialkyl phosphenium cations: applications in homogeneous gold catalysis" J. Petuškova, H. Bruns, M. Alcarazo, Angew. Chem. 2011, 123, 34883; Angew. Chem. Int. Ed. 2011, 50, 3799.

    29. "On the metallic nature of carbon in allenes and heterocumulenes" M. Alcarazo, Dalton Trans. 2011, 40, 1839.

    28. "Metal complexes with carbene ligands stabilized by lateral enamines" M. Alcarazo, K. Radkowski, R. Goddard, A. Fürstner, Chem. Commun. 2011, 47, 776.

2010

    27. "Heterocyclic S–S bond cleavage by a purely carbogenic frustrated Lewis pair" B. Inés, S. Holle, R. Goddard, M. Alcarazo, Angew. Chem. 2010, 122, 8567; Angew. Chem. Int. Ed. 2010, 49, 8389.

    26. "A new class of singlet carbene ligands" M. Alcarazo, R. M. Suárez, R. Goddard, A. Fürstner, Chem.–Eur. J. 2010, 16, 9746.

    25. "Protecting-group-free and catalysis-based total synthesis of the ecklonialactones" V. Hickmann, M. Alcarazo, A. Fürstner, J. Am. Chem. Soc. 2010, 132, 11042.

    24. "Exploring the reactivity of carbon (0)/borane-based frustrated Lewis pairs" M. Alcarazo, C. Gomez, S. Holle, R. Goddard, Angew. Chem. 2010, 122 ,5924 [Erratum: Angew. Chem. 2010, 122, 5730]; Angew. Chem. Int. Ed. 2010, 49, 5788 [Erratum: Angew. Chem. Int. Ed. 2010, 49, 5597].

    23. "Stereoselective synthesis of cationic heterobidentate C(NHC)/SR rhodium(I) complexes using stereodirecting N,N-dialkylmaino groups" A. Ros, M. Alcarazo, D. Monge, E. Álvarez, R. Fernández, J. M. Lassaletta, Tetrahedron: Asymmetry 2010, 21, 1557.

    22. "Synthesis and coordination properties of nitrogen(I)-based ligands" H. Bruns, M. Patil, J. Carreras, A. Vázquez, W. Thiel, R. Goddard, M. Alcarazo, Angew. Chem. 2010, 122, 3762; Angew. Chem. Int. Ed. 2010, 49, 3680.

    21. "Steering the surprisingly modular π-acceptor properties of N-heterocyclic carbenes: Implications for gold catalysis" M. Alcarazo, T. Stork, A. Anoop, W. Thiel, A. Fürstner, Angew. Chem. 2010, 122, 2596; Angew. Chem. Int. Ed. 2010, 49, 2542.

2009

    20. "Synthesis, structure and properties of [1,2,4]triazolo[4,3-a]pyridin-3-ylidene rhodium and palladium complexes" J. Iglesias-Sigüenza, A. Ros, E. Díez, M. Alcarazo, E. Álvarez, R. Fernández, J. M. Lassaletta, Dalton Trans. 2009, 7113.

    19. "Tetrakis(dimethylamino)allene" A. Fürstner, M. Alcarazo, H. Krause, Org. Synth. 2009, 86, 298.

    18. "Coordination Chemistry at Carbon" M. Alcarazo, C. W. Lehmann, A. Anoop, W. Thiel, A. Fürstner, Nat. Chem. 2009, 1, 295.

2008

    17. "Stereoselective synthesis of Rh(I) 4-(dialkylamino)triazol-5-yledene complexes" A. Ros, M. Alcarazo, J. Iglesias-Sigüenza, E. Díez, E. Álvarez, R. Fernández, J. M. Lassaletta, Organometallics 2008, 27, 4555.

    16. "Carbenes stabilized by ylides: pushing the limits" A. Fürstner, M. Alcarazo, K. Radkowski , W. Lehmann, Angew. Chem. 2008, 120, 8426; Angew. Chem. Int. Ed. 2008, 47, 8302.

    15. "Coordination chemistry of ene-1,1-diamines and a prototype "carbodicarbene"" A. Fürstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. 2008, 120, 3254; Angew. Chem. Int. Ed. 2008, 47, 3210.

    14. "Preparation of a non-symmetrical imidazolium salt: 1-adamantyl-3-mesityl-4,5-dimethylimidazaloium tetrafluoroborate" A. Fürstner, M. Alcarazo, V. César, H. Krause, Org. Synth. 2008, 85, 34.

2007

    13. "Effective modulation of the donor properties of N-heterocyclic carbene ligands by "through-space" communication within a planar chiral scaffold" A. Fürstner, M. Alcarazo, H. Krause, C. W. Lehmann, J. Am. Chem. Soc. 2007, 129, 12676.

    12. "Enantioselective conjugate addition of N,N-dialkylhydrazones to α-hydroxy enones" D. Monge, E. Martín-Zamora, J. Vázquez, M. Alcarazo, E. Álvarez, R. Fernández, J. M. Lassaletta, Org. Lett. 2007, 9, 2867.

    11. "Imidazo[1,5-a]pyridin-3-ylidene/thioether mixed C/S ligands and complexes thereof" S. J. Roseblade, A. Ros, D. Monge, M. Alcarazo, E. Álvarez, J. M. Lassaletta, R. Fernández, Organometallics 2007, 26, 2570.

    10. "Isoquinolin-1-ylidenes as electronically tuneable ligands" S. Gómez-Bujedo, M. Alcarazo, C. Pichon, E. Álvarez, R. Fernández, J. M. Lassaletta, Chem. Commun. 2007, 1180.

2005-2006

    9. "Synthesis, structure and applications of N-dialkylamino-N’-alkylimidazol-2-ylidenes as a new type of NHC ligands" A. Ros, D. Monge, M. Alcarazo, E. Álvarez, J. M. Lassaletta, R. Fernández, Organometallics 2006, 25, 6039.

    8. "Convenient, scalable and flexible method for the preparation of imidazolium salts with previously inaccessible substitution patterns" A. Fürstner, M. Alcarazo, V. César, C. W. Lehmann, Chem. Commun. 2006, 2176.

    7. "Synthesis, structure and electronic properties of N-dialkylamino and N-alkoxy-1,2,4-triazol-3-ylidene ligands" M. Alcarazo, R. Fernández, E. Álvarez, J. M. Lassaletta, J. Organomet. Chem. 2005, 690, 5979.

    6. "Magnesium bis(monoperoxyphathalate) hexahydrate (MMPP)" M. Alcarazo Velasco, Synlett 2005, 1807.

    5. "Imidazo[1,5-a]pyridine: A versatile architecture for N-Heterocyclic carbenes" M. Alcarazo, S. J. Roseblade, A. R. Cowley, R. Fernández, J. M. Brown, J. M. Lassaletta, J. Am. Chem. Soc. 2005, 127, 3290.

2001-2004

    4. "1,3-Bis(N,N-dialkylamino)imidazolin-2-ylidenes: synthesis and reactivity of a new family of stable N-heterocyclic carbenes" M. Alcarazo, S. J. Roseblade, E. Alonso, R. Fernández, E. Alvarez, F. J. Lahoz, J. M. Lassaletta, J. Am. Chem. Soc. 2004, 126, 13242.

    3. "Glyoxal bis-hydrazones: a new family of nitrogen ligands for asymmetric catalysis" J. M. Lassaletta, M. Alcarazo, R. Fernández, Chem. Commun. 2004, 298.

    2. "Synthesis and spectroelectrochemical studies of mixed heteroleptic chelate complexes of ruthenium (II) with 1,8-bis(2-pyridyl)-3,6-dithiaoctane (pdto) and substituted 1,10-phenanthrolines" L. A. Ortiz-Frade, L. Ruiz-Ramírez, I. González, A. Marín-Becerra, M. Alcarazo, J. G. Alvarado-Rodriguez, R. Moreno-Esparza, Inorg. Chem. 2003, 42, 1825.

    1. "Synthesis of α-hydroxyhydrazones from aldehydes" R. Fernández, E. Martín-Zamora, C. Pareja, M. Alcarazo, J. Martín, J. M. Lassaletta, Synlett 2001, 1158.

 

Research Topics

Design and Synthesis of Unconventional Ligands
Design and Synthesis of Unconventional Ligands

Design and Synthesis of Unconventional Ligands

It is well established that the reactivity of a metal can be dramatically modulated by the appropriate ligand selection. Typical ligands used in organometallic chemistry and catalysis are phosphines, CO, isonitriles, imines… More recently N-heterocyclic carbenes, a family of compounds based on low valent C(II), have gained a prominent role in the area due to their powerful electron donor ability. This property has led to a tremendous rate enhancement for some catalytic processes, in particular cross-coupling reactions or olefin metathesis. Surprisingly, the use of ligands based on other main group elements in low oxidation state, such as N(I), P(I), Si(II) and Ge(II), is still scarce even though they may be more electron releasing than carbenes. It is the objective of this project to synthesize some of these compounds and to study their coordination chemistry and possible applications in catalysis.

Design, Synthesis and Applications of Organic Frustrated Lewis Pairs
Design, Synthesis and Applications of Organic Frustrated Lewis Pairs

Design, Synthesis and Applications of Organic Frustrated Lewis Pairs

The combination of sterically demanding Lewis acids and bases does not produce the classical neutralization reaction to form Lewis adducts. Instead the unquenched acidity and basicity that coexist in the same media are able to promote unexpected reactions such as the heterolytic cleavage of dihydrogen or the activation of carbon dioxide. However, most of the known “frustrated Lewis pairs” (FLP) rely on P-, C- or N-based Lewis bases combined with a polyfluorinated borane. As an alternative to B(C6F5)3 we have employed electron poor allenes. In these compounds the intrinsic charge separation resulting from the tendency of the substituents to accept electronic density generates a partial carbocationic character on the allene central carbon, rendering this center a potential borane surrogate.

 

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