Constructing Mononuclear Palladium Catalysts by Precoordination/Solvothermal Polymerization: Recyclable Catalyst for Regioselective Oxidative Heck Reactions.

Heterogeneous, metal, single-site catalysts often exhibit higher catalytic performance than other catalysts because of their maximized atom efficiency of 100 %. Reported herein is a precoordination/solvothermal polymerization strategy to fabricate a stable mononuclear Pd-metalized porous organic polymer catalyst (Pd@POP). Pd@POP was easy to use in regioselective organic reactions because the internal structure of this Pd@POP can be easily modified.

Palladium-metalated porous organic polymers as recyclable catalysts for chemoselective decarbonylation of aldehydes.

A novel palladium nanoparticle (NP)-metalated porous organic ligand (Pd NPs/POL-xantphos) has been prepared for the chemoselective decarbonylation of aldehydes. This heterogenous catalyst not only has excellent catalytic activity and chemoselectivity, but also holds high activity after 10 runs of reuse. The effective usage of this method is demonstrated through the synthesis of biofuels such as furfuryl alcohol (FFA) via the highly chemoselective decarbonylation of biomass-derived 5-hydroxy-methylfurfural (HMF) with a TON up to 1540.

Thiophene-Alkyne-Based CMPs as Highly Selective Regulators for Oxidative Heck Reaction.

Thiophenes containing an adjacent C≡C group as ligands for Pd-promoted organic reactions are reported for the first time. These ligands were utilized as catalytic sites and integrated into the skeleton of conjugated microporous polymers. By employing these CMP materials as selective regulators, oxidative Heck reactions between arylboronic esters and electronically unbiased alkenes provide highly selective linear products.

Conjugated Microporous Polymer as Heterogeneous Ligand for Highly Selective Oxidative Heck Reaction.

A series of pyridine-type ligands containing C≡C bonds were designed and synthesized for selective oxidative Heck reaction. These ligands were utilized as functional units and integrated into the skeleton of conjugated microporous polymers. 6,6'-diiodo-2,2'-bipyridine and 1,3,5-triethynylbenzene were polycondensed via Sonogashira cross-coupling strategy to afford CMP-1 material.