个人简介
Academic Career
2011 – today Professor (Synthesis & Catalysis), Technische Universität Berlin, Berlin / Germany
2006 – 2011 Professor (Organic Chemistry), Westfälische Wilhelms-Universität Münster, Münster / Germany
2001 – 2005 Habilitation, Albert-Ludwigs-Universität Freiburg, Freiburg im Breisgau / Germany (Prof. Dr. Reinhard Brückner)
1999 – 2001 Postdoc, University of California at Irvine, Irvine / USA (Prof. Dr. Larry E. Overman)
1996 – 1999 PhD, Westfälische Wilhelms-Universität Münster, Münster / Germany (Prof. Dr. Dieter Hoppe)
1991 – 1996 Diploma, Philipps-Universität Marburg, Marburg an der Lahn / Germany (Prof. Dr. Paul Knochel)
Visiting Professorships
2018 Kyoto University, Kyoto / Japan (w/ Prof. Dr. Michinori Suginome)
2010 Australian National University, Canberra / Australia (w/ Prof. Dr. Michael S. Sherburn)
2005 Cardiff University, Cardiff / Wales (w/ Prof. Dr. Thomas Wirth)
Activities
2019 – today Chemical Science (Royal Society of Chemistry), Editorial Advisory Board
2019 – today Chemical Society Reviews (Royal Society of Chemistry), Editorial Advisory Board
2016 – 2023 Mitglied des Vorstandes der Liebig-Vereinigung (Gesellschaft Deutscher Chemiker)
2016 – 2018 Organometallics (American Chemical Society),Editorial Advisory Board
2013 – today European Journal of Organic Chemistry (ChemPubSoc Europe), International Advisory Board
2009 – today Science of Synthesis, Knowledge Updates (Thieme Publishers), Editor (Volume 4, Silicon Chemistry)
Awards / Fellowships
2018 45th IOCF Lectureship
2018 JSPS Invitational Fellowship for Research in Japan
2015 David Ginsburg Memorial Lecture, Technion, Haifa/Israel
2013 Steinhofer Lecture, Albert-Ludwigs-Universität Freiburg, Freiburg im Breisgau/Germany
2011 "Goldener Brendel" Wanderpreis für hervorragende Lehre, Westfälische Wilhelms-Universität Münster/Germany
2006 ORCHEM-Preis für Naturwissenschaftler, Liebig-Vereinigung der GDCh
2005 ADUC-Jahrespreis für Habilitanden 2004
2004 Förderpreis der Dr.-Otto-Röhm-Gedächtnisstiftung
2002 Thieme Journal-Preis
2011 – today Einstein-Professur der Einstein-Stiftung Berlin
2006 – 2008 Karl Winnacker-Stipendium, Aventis Foundation
2001 – 2006 Emmy Noether-Nachwuchsgruppe der Deutschen Forschungsgemeinschaft (Oe 249/2-1, 2, 3 and 4)
1999 – 2001Emmy Noether-Forschungsstipendium der Deutschen Forschungsgemeinschaft (Oe 249/1-1)
1997 – 1999 Kekulé-Stipendium des Fonds der Chemischen Industrie
研究领域
Cooperative Bond Activation of Interelement Bonds
We recognized at an early stage that transition-metal alkoxides/hydroxides are perfectly suited to react with various interelement bonds through σ-bond-metathesis-type processes. With our focus on synthetic silicon chemistry, we were particularly interested in the transmetalation of the silicon–boron linkage that yields a transition-metal silanide along with a boron byproduct. The catalytically generated silicon nucleophile then participates in nearly all typical asymmetric carbon–silicon bond-forming reactions, and we have been able to solve several long-standing challenges in enantioselective catalysis involving silicon, e.g., conjugate addition and allylic substitution.
The same concept is the basis for our “bioinspired” approach to the catalytic generation of silicon (and boron) electrophiles. Similar to the dihydrogen activation mechanism of hydrogenases, we accomplished the heterolytic splitting of silicon/boron–hydrogen bonds at transition-metal thiolates into sulfur-stabilized silicon/boron cations and a transition-metal hydride. As before, the activation mode is best described as a σ-bond metathesis. By this, we have been able to develop several unique transformations, e.g., electrophilic aromatic substitution with release of dihydrogen to achieve C–H bond silylation and borylation as well as partial reduction of pyridines and related benzannulated congeners.
Intramolecularly Stabilized Silicon Cations in Lewis Acid Catalysis
Our laboratory designed a new type of silicon cation where the electron deficiency at the silicon atom is compensated by the metallocenyl group, not by the metal center alone. An extreme dip angle of the silicon atom toward the metal atom is explained by two three-center/two-electron bonds with participation of both the upper and lower cyclopendienyl rings of the metallocene sandwich structure. Silicon cations of this family are strong Lewis acids and exceptionally potent in Lewis acid catalysis, e.g., difficult Diels–Alder reactions at ambient or even lower temperatures.
Main-Group Lewis Acids for Si–H and H–H Bond Activation
With our expertise in silicon chemistry and Lewis acid catalysis, we became involved in the recent topic of frustrated Lewis pair (FLP) chemistry. Our contribution lies in the preparation of new chiral derivatives of the electron-deficient boron Lewis acid B(C6F5)3 and their application in enantioselective reduction of C=X bonds. Also, we are investigating the mechanisms of the Si–H bond activation and subsequent steps both experimentally and spectroscopically (see below).
Transition-Metal-Free Transfer Hydrosilylation and Hydrogenation
We recently discovered that substituted cyclohexa-1,4-dienes are excellent surrogates for hydrosilanes (with the silicon group in one of the bisallylic positions) and dihydrogen, respectively. Treatment of these precursors with strong main-group Lewis acids leads to hydride abstraction from the methylene group, thereby generating a Wheland intermediate that either releases a silylium ion or proton. The net reaction is a two-step formation of H–/Si+ or H–/H+. The latter is rather unexpected as the corresponding Wheland complex is a high-energy intermediate. These processes have been coupled with reductions catalyzed by the same Lewis acid. Ionic transfer hydrosilylation had been totally unprecedented, and transition metal-free transfer hydrogenation employing cyclohexa-1,4-dienes as reducing agents is exceptionally rare.
Investigation of Reaction Mechanisms
Our group’s track record of mechanistic work is documented by a series of high-level publications in diverse areas of catalysis. We usually rely on experimental and spectroscopic techniques and, if needed, seek collaboration with theoretical groups (Stefan Grimme and Martin Kaupp in recent years). Early work made use of silicon-stereogenic hydrosilanes as stereochemical probes in transition-metal- as well as main-group-catalyzed hydrosilylation reactions. More recently, we were also able to implement our knowledge in silicon cation chemistry to synthesize key intermediates and test their kinetic competence in catalytic cycles. These investigations have been crucial in the mechanistic understanding of fundamental processes such as catalysis with B(C6F5)3 (and related FLP chemistry) and Brookhart’s pincer complex.
C–H Bond Activation by Oxidative Palladium Catalysis
Over the course of the years, we have tackled less-conventional topics in the rapidly developing field of C–H bond activation. Our major focus is on C–H bond alkenylation, and we are currently elaborating procedures for the site-selective C–H bond functionalization of the indole core. Broadly applicable C-7-selective arylations and alkenylations have already been reported by us. Another open challenge in C–H bond alkenylation is control over the double bond geometry with internal alkenes as coupling partners. The poor reactivity of substituted alkenes is also problematic. By the use of an alkene tethered to the directing group (DG), we realized an unusual endo ring closure; cleavage of the tether afforded fully substituted alkenes with complete diastereocontrol.
近期论文
查看导师新发文章
（温馨提示：请注意重名现象，建议点开原文通过作者单位确认）
J. C. L. Walker, H. F. T. Klare, and M. Oestreich, The power of cationic silicon Lewis acids in catalysis (Perspective),submitted for publication.
Q. Wu, A. Roy, E. Irran, Z.-W. Qu, S. Grimme, H. F. T. Klare, and M. Oestreich, Catalytic Difunctionalization of Unactivated Alkenes with Unreactive Hexamethyldisilane through Regeneration of Silylium Ions,submitted for publication.
T. Kaicharla, B. M. Zimmermann, M. Oestreich, and J. F. Teichert, Using alcohols as simple H2-equivalents for copper-catalysed transfer hydrogenations, ChemRxiv 2019, DOI: 10.26434/chemrxiv.9731279.v1.
L. Zhang and M. Oestreich, Copper-Catalyzed Enantio- and Diastereoselective Addition of Silicon Nucleophiles to 3,3-Disubstituted Cyclopropenes,submitted for publication.
J. C. L. Walker and M. Oestreich, Lewis Acid-Catalyzed Transfer Hydromethallylation for the Construction of Quaternary Carbon Centers, Angew. Chem. Int. Ed. 2019, 58, early view on August 26, 2019. (Abstract)
J.-J. Feng, Y. Xu, and M. Oestreich, Ligand-Controlled Diastereodivergent, Enantio- and Regioselective Copper-Catalyzed Hydroxyalkylboration of 1,3-Dienes with Ketones, Chem. Sci. 2019, 10, first published on August 20, 2019. (Abstract)Chosen as ChemSci Pick of the Week!Selected for the 2019 Chemical Science HOT Article Collection (open access)
S. C. Richter and M. Oestreich, Emerging Strategies for C–H Silylation (Review),Trends Chem. 2019, 1, online now on August 7, 2019. (Abstract)
P. Shaykhutdinova, S. Keess, and M. Oestreich, Cationic Silicon-Based Lewis Acids in Catalysis, in Organosilicon Chemistry – Novel Approaches and Reactions (Eds.: T. Hiyama, M. Oestreich), Wiley-VCH, Weinheim, 2019, in press (scheduled for October 14, 2019).
F. Forster and M. Oestreich, Metal-Ligand Cooperative Si–H Bond Activation, in Organosilicon Chemistry – Novel Approaches and Reactions (Eds.: T. Hiyama, M. Oestreich), Wiley-VCH, Weinheim, 2019, in press (scheduled for October 14, 2019).
Q. Wu, E. Irran, R. Müller, M. Kaupp, H. F. T. Klare, and M. Oestreich, Characterization of hydrogen-substituted silylium ions in the condensed phase,Science 2019, 365, 168-172. (Abstract) Highlighted in Nachr. Chem. 2019, 67, 47.
W. Mao, W. Xue, E. Irran, and M. Oestreich, Copper-Catalyzed Regio- and Enantioselective Addition of Silicon Grignard Reagents to Alkenes Activated by Azaaryl Groups, Angew. Chem. 2019, 131, 10833-10836; Angew. Chem. Int. Ed. 2019, 58, 10723-10726. (Abstract)Selected as a "Hot Paper" by Angewandte Chemie.(open access) Highlighted in SYNFACTS 2019, 15, 1024.
J. Seliger and M. Oestreich, Making the Silylation of Alcohols Chiral: Asymmetric Protection of Hydroxy Groups (Minireview),[OMCOS 20 Special Collection] Chem. Eur. J. 2019, 25, 9358-9365. (Abstract)
S. C. Richter and M. Oestreich, Bioinspired Metal-Free Formal Decarbonylation of α-Branched Aliphatic Aldehydes at Ambient Temperature, Chem. Eur. J. 2019, 25, 8508-8512. (Abstract)
W. Chen and M. Oestreich, Metal-Free Transfer Hydrobromination of C–C Triple Bonds,Org. Lett. 2019, 21, 4531-4534. (Abstract)
J.-J. Feng and M. Oestreich, Tertiary α-Silyl Alcohols by Diastereoselective Coupling of 1,3-Dienes and Acylsilanes Initiated by Enantioselective Copper-Catalyzed Borylation, Angew. Chem. 2019, 131, 8295-8299; Angew. Chem. Int. Ed. 2019, 58, 8211-8215. (Abstract) Highlighted in SYNFACTS 2019, 15, 889.
H. Yi and M. Oestreich, Regiodivergent and Stereospecific Aziridine Opening by Copper-Catalyzed Addition of Silicon Grignard Reagents, Chem. Eur. J. 2019, 25, 6505-6507. (Abstract) Selected as a "Hot Paper" by Chemistry - A European Journal.
W. Xue, W. Mao, L. Zhang, and M. Oestreich, Mechanistic Dichotomy of Magnesium- and Zinc-Based Germanium Nucleophiles in the C(sp3)–Ge Cross-Coupling with Alkyl Electrophiles, Angew. Chem. 2019, 131, 6506-6509; Angew. Chem. Int. Ed. 2019, 58, 6440-6443. (Abstract)
P. Shaykhutdinova and M. Oestreich, Further Structural Modification of Sulfur-Stabilized Silicon Cations with Binaphthyl Backbones,Synthesis 2019, 51, 2221-2229. (Abstract)
P. Orecchia, W. Yuan, and M. Oestreich, Transfer Hydrocyanation of α- and α,β-Substituted Styrenes Catalyzed by Boron Lewis Acids, Angew. Chem. 2019, 131, 3617-3621; Angew. Chem. Int. Ed. 2019, 58, 3579-3583. (Abstract)
H. Yi, W. Mao, and M. Oestreich, Enantioselective Construction of α-Chiral Silanes by Nickel-Catalyzed C(sp3)–C(sp3) Cross-Coupling, Angew. Chem. 2019, 131, 3613-3616; Angew. Chem. Int. Ed. 2019, 58, 3575-3578. (Abstract) Highlighted in SYNFACTS 2019, 15, 506.
京公网安备 11010802027423号