Coordination Chemistry and Asymmetric Homogeneous Catalysis
Manuel Alcarazo has moved to the University of Göttingen as Professor for Organic Chemistry in December 2015. Information on his current research is available here. This web page documents the activities of his group at the Max-Planck-Institut für Kohlenforschung (until 2015).
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.
Dr. Manuel Alcarazo
- since 2015
- Professor for Organic Chemistry at Georg-August University Göttingen
- 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
- 2013
- Young Scientist Award from the Academy of Sciences of Göttingen
- 2013
- ADUC Annual Prize for Habilitands 2012
- 2013
- Science Award of the Industrie-Club Duesseldorf and the North Rhine-Westphalian Academy of Sciences, Humanities and the Arts
- 2013-2017
- Lecturer's scholarship ("Dozentenstipendium") of the Chemical Industry Fund
- 2012
- Sponsorship Award of Dr. Otto Roehm Commemoration Foundation
- 2011
- European Research Council Starting Grant for his research “Activation 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
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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 2014
- Member of the Editorial Advisory Board of "Organometallics"
- since 2009
- Member of Global Young Faculty
- since 2008
- Group leader at the Max-Planck-Institut für Kohlenforschung
-
Organometallic Chemistry (II), TU Dortmund, WS 2013/2014
Organometallic Chemistry (I), TU Dortmund, SS 2013
Stereoselective Synthesis, Heinrich-Heine University Düsseldorf, SS 2012
Total Synthesis (I), TU Dortmund, WS 2011/2012
Stereoselective Synthesis (II), TU Dortmund, SS 2011
Stereoselective Synthesis (I), TU Dortmund, WS 2010/2011
Principles in Organometallic Chemistry, TU Dortmund, SS 2010
Total Synthesis (I), TU Dortmund, WS 2009/2010
Research Topics
- Cationic ligands: synthesis and applications of extreme π-acid catalysts
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Cationic ligands: synthesis and applications of extreme π-acid catalysts
The goal of this project is the synthesis of extreme π-acceptor phosphines through the introduction of positively charged homo- or heteroaromatic substituents directly attached to the phosphorus atom. By exploiting this property, new Au and Pt catalysts have been developed that display a dramatically enhanced capacity to activate π-systems.
Very recently, we reported the synthesis of the first ever isolated carbene-stabilized P1-centered trication [L3P]3+ (L = 2,3-dialkylaminocyclopropenium) 1 by reaction of the 1-chloro-2,3-(dimethylamino) cyclopropenium salt 2 and P(SiMe3)3 (Scheme 1). Despite the three positive charges on the groups directly attached to the P atom, this compound can still serve as a ligand for π-acidic metals such as Pt. Thus, when 1 is treated with K2PtCl4 in acetonitrile, the bench stable complex 3 is formed. More interestingly, charge decomposition analysis of the metal-ligand interaction in 3 gave the surprising result that the total L→M σ-donation (0.31 e) is lower than the L→M π-back donation (0.43 e) into the very low-lying LUMO of 1, which must hence be regarded as the main interaction in 3. This unconventional situation in which the P-ligand removes net electron density from the metal suggests that compound 1 increases the natural π-acidity of Pt(II) centers. It should thus accelerate known reactions, or even permit new ones, in which either the coordination of the substrate or the nucleophilic attack to the activated substrate are the rate-determining steps.
Accordingly, we chose for our studies on ligand effects a series of phosphanes such as PPh3, P(OPh)3, P(C6F5)3 and precatalyst 3 in combination with a silver salt. As expected, both P(OPh)3 and P(C6F5)3 performed better than PPh3 in terms of reactivity (Scheme 2).
In addition, our synthetic program has already benefitted from these novel tools and natural products such as Orchinol, Ochrolide, Bulbophyllantrin and Epimedoicarisoside A have been prepared using our Pt and Au catalysts for the key hydroarylation step (Scheme 3).
- Synthesis and applications of simultaneous σ- and π-donor ligands: C-M dative double bonds
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Synthesis and applications of simultaneous σ- and π-donor ligands: C-M dative double bonds
In this area, our research has been strongly inspired by the theoretical work of Frenking about the nature of carbodiphosphorane 1 (Scheme 1). His studies revealed that in compound 1 and analogues the central carbon atom retains its four valence electrons that are thus all available for coordination. In fact, carbodiphosphoranes are known to react with two Lewis acids such as AuCl affording diaurated derivatives. However, their ability to donate their four electrons to the same electrophile in a simultaneous σ- and π-donation had not been described.
In this regard, we envisaged that the use carbodiphosphoranes may provide sufficient stabilization to attenuate the reactivity and allow the isolation of dihydrido borenium cations [L→BH2]+ (L = carbodiphosphorane), a series of compounds that cannot be isolated when classical σ-donating ligands are employed.
Our strategy is already producing some positive results with other low valent cations. Up to now we have been able to synthesize compound 4 which already depicts a σ- and π-dative bond between the central carbon atom and the GeCl moiety. Reaction with dimethylamino pyridine affords adduct 5 where the π interaction is not existing anymore.
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