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Synthesis of extremely active pincer-type suzuki catalysts bearing amino-phosphine ligands and their potential applicability in C-H activation processes

Applicant Frech Christian
Number 126633
Funding scheme Project funding (Div. I-III)
Research institution Institut für Chemie Universität Zürich
Institution of higher education University of Zurich - ZH
Main discipline Inorganic Chemistry
Start/End 01.10.2009 - 30.09.2011
Approved amount 129'260.00
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All Disciplines (2)

Discipline
Inorganic Chemistry
Organic Chemistry

Keywords (4)

catalysis; palladium; C-C bond formation; pincer

Lay Summary (English)

Lead
Lay summary
palladium catalyzed C-C cross coupling reaction belong to the most important C-C bond forming reactions in organic chemistry. Although various catalysts have been discovered during the last decades the development of new systems is of high importance. We were able to synthesize a new class of pincer complexes, which turned out to be extremely efficient Suzuki- and Heck-catalysts e.g.. Their synthesis is extremely facile and was made from very cheap starting materials within only few hours. We could show that the catalyst solutions can directly be used to catalyze the above mentioned reactions. Further improvements are ongoing to explore the scope of our catalyst. We hope that our system once might be a standard catalyst in organic laboratories.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Observation of Binuclear Palladium Clusters upon ESI-MS Monitoring of the Suzuki-Miyaura Cross-Coupling Catalyzed by a Dichloro-bis(aminophosphine) Complex of Palladium
Agrawal D, Schroder D, Frech CM (2011), Observation of Binuclear Palladium Clusters upon ESI-MS Monitoring of the Suzuki-Miyaura Cross-Coupling Catalyzed by a Dichloro-bis(aminophosphine) Complex of Palladium, in ORGANOMETALLICS, 30(13), 3579-3587.
Access to 2-Aminopyridines - Compounds of Great Biological and Chemical Significance
Bolliger JL, Oberholzer M, Frech CM (2011), Access to 2-Aminopyridines - Compounds of Great Biological and Chemical Significance, in ADVANCED SYNTHESIS & CATALYSIS, 353(6), 945-954.
[Pd(Cl)(2){P(NC5H10)(C6H11)(2)}(2)]-A Highly Effective and Extremely Versatile Palladium-Based Negishi Catalyst that Efficiently and Reliably Operates at Low Catalyst Loadings
Bolliger JL, Frech CM (2010), [Pd(Cl)(2){P(NC5H10)(C6H11)(2)}(2)]-A Highly Effective and Extremely Versatile Palladium-Based Negishi Catalyst that Efficiently and Reliably Operates at Low Catalyst Loadings, in CHEMISTRY-A EUROPEAN JOURNAL, 16(36), 11072-11081.
Dichloro-Bis(aminophosphine) Complexes of Palladium: Highly Convenient, Reliable and Extremely Active Suzuki-Miyaura Catalysts with Excellent Functional Group Tolerance
Bolliger JL, Frech CM (2010), Dichloro-Bis(aminophosphine) Complexes of Palladium: Highly Convenient, Reliable and Extremely Active Suzuki-Miyaura Catalysts with Excellent Functional Group Tolerance, in CHEMISTRY-A EUROPEAN JOURNAL, 16(13), 4075-4081.
Pincer-Type Heck Catalysts and Mechanisms Based on Pd-IV Intermediates: A Computational Study
Blacque O, Frech CM (2010), Pincer-Type Heck Catalysts and Mechanisms Based on Pd-IV Intermediates: A Computational Study, in CHEMISTRY-A EUROPEAN JOURNAL, 16(5), 1521-1531.
The 1,3-Diaminobenzene-Derived Aminophosphine Palladium Pincer Complex {C6H3[NHP(piperidinyl)(2)](2)Pd(Cl)} - A Highly Active Suzuki-Miyaura Catalyst with Excellent Functional Group Tolerance
Bolliger JL, Frech CM (2010), The 1,3-Diaminobenzene-Derived Aminophosphine Palladium Pincer Complex {C6H3[NHP(piperidinyl)(2)](2)Pd(Cl)} - A Highly Active Suzuki-Miyaura Catalyst with Excellent Functional Group Tolerance, in ADVANCED SYNTHESIS & CATALYSIS, 352(6), 1075-1080.
Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions
Bolliger JL, Frech CM (2009), Aminophosphine Palladium Pincer Complexes for Suzuki and Heck Reactions, in CHIMIA, 63(1-2), 23-28.
Highly Convenient, Clean, Fast, and Reliable Sonogashira Coupling Reactions Promoted by Aminophosphine-Based Pincer Complexes of Palladium Performed under Additive-and Amine-Free Reaction Conditions
Bolliger JL, Frech CM (2009), Highly Convenient, Clean, Fast, and Reliable Sonogashira Coupling Reactions Promoted by Aminophosphine-Based Pincer Complexes of Palladium Performed under Additive-and Amine-Free Reaction Conditions, in ADVANCED SYNTHESIS & CATALYSIS, 351(6), 891-902.
Transition metal-free amination of aryl halides-A simple and reliable method for the efficient and high-yielding synthesis of N-arylated amines
Bolliger JL, Frech CM (2009), Transition metal-free amination of aryl halides-A simple and reliable method for the efficient and high-yielding synthesis of N-arylated amines, in TETRAHEDRON, 65(6), 1180-1187.
Transition metal-free amination of aryl halides-A simple and reliable method for the efficient and high-yielding synthesis of N-arylated amines
Bolliger JL, Frech CM (2009), Transition metal-free amination of aryl halides-A simple and reliable method for the efficient and high-yielding synthesis of N-arylated amines, in TETRAHEDRON, 65(6), 1180-1187.
Rationally designed pincer-type Heck catalysts bearing aminophosphine substituents: Pd-IV intermediates and palladium nanoparticles
Bolliger JL, Blacque O, Frech CM (2008), Rationally designed pincer-type Heck catalysts bearing aminophosphine substituents: Pd-IV intermediates and palladium nanoparticles, in CHEMISTRY-A EUROPEAN JOURNAL, 14(26), 7969-7977.
Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II)
Bolliger JL, Blacque O, Frech CM (2007), Bis[2,6-bis(dipiperidin-1-ylphosphanyloxy)phenyl]bromidopalladium(II), in ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 63, 3086-2051.
Short, facile, and high-yielding synthesis of extremely efficient pincer-type suzuki catalysts bearing aminoiphosphine substituents
Bolliger JL, Blacque O, Frech CM (2007), Short, facile, and high-yielding synthesis of extremely efficient pincer-type suzuki catalysts bearing aminoiphosphine substituents, in ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 46(34), 6514-6517.

Associated projects

Number Title Start Funding scheme
116062 Synthesis of Extremely Active Pincer-Typ Suzuki Catalysts Bearing Amino-phosphine Ligands and their Potential Applicability in C-H Activation Processes 01.05.2007 Project funding (Div. I-III)
137660 Synthesis of extremely active pincer-type suzuki catalysts bearing amino-phosphine ligands and their potential applicability in C-H activation processes 01.09.2014 Project funding (Div. I-III)
116062 Synthesis of Extremely Active Pincer-Typ Suzuki Catalysts Bearing Amino-phosphine Ligands and their Potential Applicability in C-H Activation Processes 01.05.2007 Project funding (Div. I-III)
137660 Synthesis of extremely active pincer-type suzuki catalysts bearing amino-phosphine ligands and their potential applicability in C-H activation processes 01.09.2014 Project funding (Div. I-III)

Abstract

We were able to synthesize a new class of pincer complexes, which turned out to be extremely efficient Suzuki- and Heck-catalysts. Their synthesis is extremely facile and can be made from very cheap starting materials within only few hours. Impressively, the catalyst solutions can directly be used to catalyze the above mentioned reactions and show essentially the same catalytic activity than catalyst solutions made from the pure catalysts. Our results indicated that PdII/PdIV mechanisms might be operative in the Suzuki reaction, whereas palladium nanoparticles are found to be the catalytically active forms in the Heck reaction. Furthermore, we are currently collaborating with the group of D. Brüehwiler (from the University of Zurich). We are currently grafting our complex on mesoporeous silica in order to carry out the so-called “3-phase-test”. Supposed the Heck reaction proceeds via palladium nanoparticles no or only slight retardation is anticipated to be obtained in that test, whereas no reaction should be obtained when the catalysts stay on the support, indicating that the catalysts are originally of homogeneous character. On the other hand, DFT calculations are ongoing with prototypic pincer catalysts, in order to figure out whether pincer-type PdIV intermediates are thermally accessible and hence could be an alternative to palladium nanoparticles as their catalytically active forms. In addition, we are will investigate further cross-coupling reactions, such as the Sonogashira cross-coupling and the Negishi-reaction. Finally, we will investigate C-H bond activation reactions of NH-functionalized precursors. In a subproject B we focus on the synthesis of aminophosphine based iron pincer complexes and their application in cross-coupling reactions. In addition, the palladium project will be continued, since the student working on subproject A will finish after 11 months.
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