Soon Hyeok Hong

1,4-Benzoquinones have been found to prevent olefin isomerization of a number of allylic ethers and long-chain aliphatic alkenes during ruthenium-catalyzed olefin metathesis reactions. Electron-deficient benzoquinones are the most effective additives for the prevention of olefin migration. This mild, inexpensive, and effective method to block olefin isomerization increases the synthetic utility of olefin metathesis via improvement of overall product yield and purity.

The decomposition of a series of ruthenium metathesis catalysts has been examined using methylidene species as model complexes. All of the phosphine-containing methylidene complexes decomposed to generate methylphosphonium salts, and their decomposition routes followed first-order kinetics. The formation of these salts in high conversion, coupled with the observed kinetic behavior for this reaction, suggests that the major decomposition pathway involves nucleophilic attack of a dissociated phosp

Dinuclear ruthenium complex, with a bridging carbide and a hydride ligand, and methyltricyclohexylphosphonium chloride result from thermal decomposition of olefin metathesis catalyst, (IMesH2)(PCy3)(Cl)2Ru=CH2. Involvement of dissociated phosphine in the decomposition is proposed. The dinuclear complex has catalytic olefin isomerization activity, which can be responsible for competing isomerization processes in certain olefin metathesis reactions.

A novel water-soluble ruthenium olefin metathesis catalyst supported by a poly(ethylene glycol) conjugated saturated 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene ligand is reported. The catalyst displays improved activity in ring-opening metathesis polymerization, ring-closing metathesis, and cross-metathesis reactions in aqueous media.

Transition metal catalyzed oxidative amide synthesis directly from primary alcohols and amines is a highly atom economical transformation that evolves hydrogen gas as the only by-product. Several Ru-, Rh-based homogeneous and Ag-based heterogeneous catalysts have been developed for direct amide synthesis. Most of the developed catalysts showed excellent activity with sterically unhindered alcohols and amines; however, limited activity was observed with sterically hindered alcohols or amines, les

Well-defined N-heterocyclic carbene based ruthenium complexes were developed as highly active catalysts for direct amide synthesis from alcohols and amines. A catalytic amount of a base such as KO t Bu was essential to initiate the catalytic cycle. Activity of the Ru complexes was comparable with the reported in situ Ru catalysts. These catalysts provided mechanistic insight suggesting a Ru hydride species as an active catalytic intermediate. The generation of the Ru hydride was critical for the

Having a breakdown: Decomposition of the olefin metathesis catalyst [(biph)(PCy3)Cl2RuC(H)Ph] (biph= N,N′-diphenylbenzimidazol-2-ylidene, Cy=cyclohexyl) results in benzylidene insertion into an ortho CH bond of an N-phenyl group of the biph ligand. The ruthenium center further inserts into another ortho CH bond of the other N-phenyl ring to give a new RuC bond as a part of a five-membered metallacycle (see scheme).

Abstract An efficient, operatively simple, acceptorless, and base‐free dehydrogenation of secondary alcohols and nitrogen‐containing heterocyclic compounds was achieved by using readily available ruthenium hydride complexes as precatalysts. The complex RuH 2 (CO)(PPh 3 ) 3 ( 1 ) and Shvo’s complex ( 2 ) showed excellent activities for the dehydrogenation of secondary alcohols and nitrogen containing heterocycles. In addition to complexes 1 and 2 , the complex RuH 2 (PPh 3 ) 4 ( 3 ) also showed m

The use of alkyl chlorides in Pd-catalyzed Mizoroki-Heck coupling reactions remains an unsolved problem despite their significant potential for synthetic utility and applicability. The combination of the high thermodynamic barrier of alkyl chloride activation and kinetic propensity of alkylpalladium complexes to undergo undesired β-hydride elimination provides significant challenges. Herein, a variety of alkyl chlorides, even tertiary chlorides, are shown to efficiently participate in Mizoroki-H

An unprecedented protocol for urea synthesis directly from methanol and amine was accomplished. The reaction is highly atom-economical, producing hydrogen as the sole byproduct. Commercially available ruthenium pincer complexes were used as catalysts. In addition, no additive, such as a base, oxidant, or hydrogen acceptor, was required. Furthermore, unsymmetrical urea derivatives were successfully obtained via a one-pot, two-step reaction.

A completely atom-economical and redox-neutral catalytic amide synthesis from an alcohol and a nitrile is realized. The amide C-N bond is efficiently formed between the nitrogen atom of nitrile and the α-carbon of alcohol, with the help of an N-heterocyclic carbene-based ruthenium catalyst, without a single byproduct. A utility of the reaction was demonstrated by synthesizing (13)C or (15)N isotope-labeled amides without involvement of any separate reduction and oxidation step.

Oxidation of alcohols is an essential organic reaction, affording versatile carbonyl groups. To provide a sustainable solution for environmentally harmful traditional oxidation methods, the transition-metal catalyzed acceptor-free dehydrogenation of alcohols has attracted much attention. The widely used catalysts for the dehydrogenation reaction are based on precious metals, which are not economical and environmentally benign. We developed an operationally simple, economical, and environmentally

A carbon capture and use (CCU) strategy was applied to organic synthesis. Carbon dioxide (CO2) captured directly from exhaust gas was used for organic transformations as efficiently as hyper-pure CO2 gas from a commercial source, even for highly air- and moisture-sensitive reactions. The CO2 capturing aqueous ethanolamine solution could be recycled continuously without any diminished reaction efficiency.

A well-defined N-heterocyclic carbene based ruthenium complex was developed as a highly active precatalyst for the direct amide synthesis from alcohols and secondary amines. Notably, reaction of 1-hexanol and dibenzylamine afforded 60% of the corresponding amide using our catalytic system, while no amide formation was observed for this reaction with the previously reported catalytic systems. Unlike the previously reported amidation with less sterically hindered alcohols and amines, involvement o

Abstract The utilizations of omnipresent, thermodynamically stable amides and aliphatic C(sp 3 )−H bonds for various functionalizations are ongoing challenges in catalysis. In particular, the direct coupling between the two functional groups has not been realized. Here, we report the synergistic activation of the two challenging bonds, the amide C−N and unactivated aliphatic C(sp 3 )−H, via metallaphotoredox catalysis to directly acylate aliphatic C−H bonds utilizing amides as stable and readily