Protocol for efficient dearomatization of N-heteroaromatics with halogen(I) complex catalyst.

In this protocol, we describe the application of a halogen(I) complex as a highly active non-metallic complex catalyst. Specifically, we present a detailed guide to synthesize the halogen(I) complex catalyst and utilize it as an anion-binding catalyst for the Mukaiyama-Mannich-type reaction of N-heteroaromatics such as pyridines. By utilizing a simple catalyst preparation approach and relatively low catalyst loading, the steps outlined in this protocol contribute to the rapid development of useful substances such as pharmaceuticals and functional materials.

Three-center-four-electron halogen bond enables non-metallic complex catalysis for Mukaiyama-Mannich-type reaction.

The three-center-four-electron halogen bond (3c4e X-bond) presents a fundamental design concept for catalysis. By integrating halogen(I) (X: I or Br), the bis-pyridyl ligand , and a non-nucleophilic counteranion Y, we developed non-metallic complex catalysts, [···X···]Ys, that exhibited outstanding activity and facilitated the Mukaiyama-Mannich-type reaction of -heteroaromatics with parts-per-million-level catalyst loading. The high activity of [···X···]SbF was clearly demonstrated.

C-H Triflation of BINOL Derivatives Using DIH and TfOH.

C-H trifluoromethanesulfonyloxylation (triflation) of 1,1'-bi-2-naphthol (BINOL) derivatives has been established under mild conditions using 1,3-diiodo-5,5-dimethylhydantoin (DIH) and trifluoromethanesulfonic acid (TfOH). Up to eight TfO groups can be introduced in a single operation. The resulting highly oxidized BINOL derivatives can be successfully converted to 8,8'-dihydroxy BINOL and bisnaphthoquinone compounds.

Amine/Hydrido Bifunctional Nanoporous Silica with Small Metal Nanoparticles Made Onsite: Efficient Dehydrogenation Catalyst.

Multifunctional catalysts are of great interest in catalysis because their multiple types of catalytic or functional groups can cooperatively promote catalytic transformations better than their constituents do individually. Herein we report a new synthetic route involving the surface functionalization of nanoporous silica with a rationally designed and synthesized dihydrosilane (3-aminopropylmethylsilane) that leads to the introduction of catalytically active grafted organoamine as well as single metal atoms and ultrasmall Pd or Ag-doped Pd nanoparticles via on-site reduction of metal ions. The resulting nanomaterials serve as highly effective bifunctional dehydrogenative catalysts for generation of H from formic acid.