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Developments and mechanistic studies of nickel-catalyzed coupling reactions of nonactivated alkyl halides

English title Developments and mechanistic studies of nickel-catalyzed coupling reactions of nonactivated alkyl halides
Applicant Hu Xile
Number 144393
Funding scheme Project funding (Div. I-III)
Research institution Institut des sciences et ingénierie chimiques EPFL - SB - ISIC
Institution of higher education EPF Lausanne - EPFL
Main discipline Inorganic Chemistry
Start/End 01.01.2013 - 31.12.2015
Approved amount 204'129.00
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Keywords (5)

pincer ligands; Nickel; C-C coupling; homogeneous catalysis; Alkyl halides

Lay Summary (English)

Lead
Lay summary
Cross coupling reactions are among the most important methods for the synthesis of fine chemicals, pharmaceuticals, and molecular materials. Nonactivated alkyl electrophiles are difficult yet highly useful reaction partners in these reactions. We propose to develop nickel-based catalysts and methods for the coupling reactions of nonactivated alkyl halides. The candidate catalysts are well-defined coordination compounds supported by various chelating amine ligands, including for example charged and neutral pincer-type ligands. In addition to Kumada coupling reactions, the candidate catalysts will be applied for other challenging but very useful reactions of nonactivated alkyl halides such as Suzuki-Miyura and Hiyama coupling reactions. A second emphasis of the project is on the mechanistic studies of these nickel-catalyzed reactions. In particular, we will focus on (a) isolation of intermediate species and investigation of their properties and reactivity under single-turnover conditions; (b) kinetic measurements of catalytic reactions using in-situ IR and/or NMR techniques. The research shall lead to not only new and useful synthetic methods, but also new principles and knowledge in catalyst design.
Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
From Dimethylamine to Pyrrolidine: The Development of an Improved Nickel Pincer Complex for Cross-Coupling of Nonactivated Secondary Alkyl Halides
Perez Garcia Pablo M., Di Franco Thomas, Epenoy Alexandre, Scopelliti Rosario, Hu* Xile (2016), From Dimethylamine to Pyrrolidine: The Development of an Improved Nickel Pincer Complex for Cross-Coupling of Nonactivated Secondary Alkyl Halides, in ACS Catalysis, 6(1), 258-261.
Nickel-catalyzed direct alkylation of terminal alkynes at room temperature: A hemilabile pincer ligand enhances catalytic activity
Pérez García Pablo M., Ren Peng, Ren Peng, Scopelliti Rosario, Hu Xile (2015), Nickel-catalyzed direct alkylation of terminal alkynes at room temperature: A hemilabile pincer ligand enhances catalytic activity, in ACS Catalysis, 5(2), 1164-1171.
Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes
Di Franco Thomas, Epenoy Alexandre, Hu Xile (2015), Synthesis of E-Alkyl Alkenes from Terminal Alkynes via Ni-Catalyzed Cross-Coupling of Alkyl Halides with B-Alkenyl-9-borabicyclo[3.3.1]nonanes, in Organic Letters, 17(19), 4910-4913.
Bimetallic oxidative addition in nickel-catalyzed alkyl-aryl Kumada coupling reactions
Breitenfeld Jan, Wodrich Matthew D., Hu Xile (2014), Bimetallic oxidative addition in nickel-catalyzed alkyl-aryl Kumada coupling reactions, in Organometallics, 33(20), 5708-5715.
Mechanistic insights into nickaminecatalyzed alkyl-alkyl cross-coupling reactions
Breitenfeld Jan, Hu Xile (2013), Mechanistic insights into nickaminecatalyzed alkyl-alkyl cross-coupling reactions, in Chimia, 68(4), 235-238.
Suzuki-miyaura cross-coupling reactions of unactivated alkyl halides catalyzed by a nickel pincer complex
Di Franco Thomas, Boutin Nicolas, Hu Xile (2013), Suzuki-miyaura cross-coupling reactions of unactivated alkyl halides catalyzed by a nickel pincer complex, in Synthesis (Germany), 45(21), 2949-2958.

Collaboration

Group / person Country
Types of collaboration
Clemence Corminboeuf, Matthew Wodrich, EPFL Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
Summer school DTU, center for individual nanoparticle functionality Talk given at a conference Base metal catalysis for energy and sustainability 14.08.2014 Kobaek strand, Denmark Hu Xile;
ACS national meeting Talk given at a conference Nickel and iron catalyzed cross coupling 10.08.2014 St. Francisco, United States of America Hu Xile;


Awards

Title Year
Young Researcher Award, European Federation of Catalysis Societies 2015
European Medal for Bio-Inorganic Chemistry (Eurobic Medal) 2014
Organometallics Young Investigator Fellowship, American Chemical Society 2014
Fellow, Royal Society of Chemistry (UK) 2014
Rising Star, International Conference on Coordination Chemistry 2014
Chemical Society Reviews Emerging Investigator Lectureship, Royal Society of Chemistry 2013
Teaching award, section of chemistry and chemical engineering, EPFL 2013

Associated projects

Number Title Start Funding scheme
126498 Ni and Pd complexes of pincer NN2 ligands for catalytic C-C and C-heteroatom bond forming reactions 01.10.2009 Project funding (Div. I-III)
162362 Synthetic and mechanistic studies of nickel-catalyzed cross coupling reactions of alkyl electrophiles using well-defined coordination complexes 01.01.2016 Project funding (Div. I-III)

Abstract

Cross coupling reactions are among the most important methods for the synthesis of fine chemicals, pharmaceuticals, and molecular materials. Nonactivated alkyl electrophiles are difficult yet highly useful reaction partners in these reactions. We propose to develop nickel-based catalysts and methods for the coupling reactions of nonactivated alkyl halides. The candidate catalysts are well-defined coordination compounds supported by various chelating amine ligands, including for example charged and neutral pincer-type ligands. In addition to Kumada coupling reactions, the candidate catalysts will be applied for other challenging but very useful reactions of nonactivated alkyl halides such as Suzuki-Miyura and Hiyama coupling reactions. A second emphasis of the project is on the mechanistic studies of these nickel-catalyzed reactions. In particular, we will focus on (a) the isolation of intermediate species and investigation of their properties and reactivity under single-turnover conditions; (b) the kinetic measurements of catalytic reactions using in-situ IR and/or NMR techniques. The research shall lead to not only new and useful synthetic methods, but also new principles and knowledge in catalyst design.
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