Heterogeneous Nickel‐Catalyzed Cross‐Coupling between Aryl Chlorides and Alkyllithiums Using a Polystyrene‐Cross‐Linking Bisphosphine Ligand

Abstract

A polystyrene-cross-linking bisphosphine ligand PS-DPPBz was used for Ni-catalyzed crosscoupling with organolithiums. A bench-stable precatalyst [NiCl 2 (PS-DPPBz)] enabled efficient coupling reactions between aryl chlorides and alkyllithiums. The heterogeneous Ni system showed good reusability. Scheme 4. Reuse of the [Ni-(PS-DPPBz)] catalyst system. Scheme 5. The reaction of 1 a and 2 a with low catalyst loading (S/C = 2000).

Porous Ligand Creates New Reaction Route: Bifunctional Single-Atom Palladium Catalyst for Selective Distannylation of Terminal Alkynes

“…The special steric hindrance and electronic effects of the ligands, as well as the overall synergistic catalytic center, improve the chemo-and stereoselectivity. [41][42][43][44][45][46][47][48][49] However, different from the previous metal-POL-catalyzed known reactions, the development of a new reaction mechanism, which is controlled by the pore enrichment of the support and high dispersion and anti-agglomeration nature of the SAS has not been explored to date. It has been difficult to achieve so far, because it requires a complete and rational adjustment of various factors, such as finding suitable reaction templates, designing reaction mechanisms, controlling metal particle size, and selecting potential carriers.…”

Nickel-Catalyzed Decarboxylation of Aryl Carbamates for Converting Phenols into Aromatic Amines

“…However, attempts to increase the yield of 2a further using 3b and 3f failed. We recently reported a new class of polymer-supported phosphine ligand, PS-DPPBz ( 3g) , which features a rigid 1,2-bis­(diphenyl­phosphino)­benzene moiety serving as a fourfold cross-linking unit on a polystyrene support . The unique constrained and isolated environment of the bisphosphine motif in 3g allows selective 1:1 complexation of a metal center with the bisphosphine unit and suppresses the undesired comproportionation induced by the encounter of two metal centers.…”

“…The unique constrained and isolated environment of the bisphosphine motif in 3g allows selective 1:1 complexation of a metal center with the bisphosphine unit and suppresses the undesired comproportionation induced by the encounter of two metal centers. Therefore, using 3g instead of simple nonsupported phosphines led to significantly higher catalytic activity in several metal-catalyzed reactions . Furthermore, ligand 3g can be readily synthesized in two steps from commercial reagents.…”

Iridium Complex Immobilized on Custom-Designed Periodic Mesoporous Organosilica as Reusable Catalyst for the Dehydrogenative Oxidation of Alcohols

“…Designing a catalyst that combines the advantageous features of both homogeneous and heterogeneous metal catalysts is clearly the way to address the above-mentioned issues and is a key requirement for the further development of catalytic chemistry. − Cooperativity between a transition metal atom and a custom-designed ligand composed of organic moiety, which is peculiar for homogeneous catalysis, is relatively unexplored in the field of heterogeneous catalysis. Hence, we assumed profitable to establish a new and efficient method for synthesizing heterogeneous catalysts having custom-designed organic ligands, which exhibit cooperative effects with the metal atoms, instead of cooperative atoms such as oxygen atoms of metal oxides, , expecting creation of new catalysts with unprecedented advantage and high performance as catalyst.…”