pincer ligands; Nickel; C-C coupling; homogeneous catalysis; 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.
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.
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.
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.
Breitenfeld Jan, Hu Xile (2013), Mechanistic insights into nickaminecatalyzed alkyl-alkyl cross-coupling reactions, in Chimia
, 68(4), 235-238.
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.
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.