Trost Reaction Research Articles

Counteranion‐Directed Catalysis in the Tsuji–Trost Reaction: Stereocontrolled Access to 2,5‐Disubstituted 3‐Hydroxy‐Tetrahydrofurans

Hydrogen bonds can play a prominent role in organometallic catalysis, as shown for the title reaction, in which a counteranion directs the cyclization through the formation of hydrogen bonds that likely involve a proton of the π-allyl/palladium species itself. The reaction allows access to four out of the eight stereoisomers of 2,5-disubstitued 3-hydroxy-tetrahydrofurans and thus fragments of complex natural products.

Counteranion‐Directed Catalysis in the Tsuji–Trost Reaction: Stereocontrolled Access to 2,5‐Disubstituted 3‐Hydroxy‐Tetrahydrofurans

Counteranion‐Directed Catalysis in the Tsuji–Trost Reaction: Stereocontrolled Access to 2,5‐Disubstituted 3‐Hydroxy‐Tetrahydrofurans

Impact of cyclodextrins on the behavior of amphiphilic ligands in aqueous organometallic catalysis

In this study, we showed that the addition of randomly modified β-cyclodextrin (RAME-β-CD) in aqueous medium could have a beneficial impact on the catalytic performances of phosphane-based aggregates in the Pd-catalyzed cleavage of allyl carbonates (Tsuji–Trost reaction). The RAME-β-CD/phosphane supramolecular interactions helped explain the catalytic results. The presence of RAME-β-CD in the aqueous compartment improved the phosphane-based aggregate dynamics. The exchanges between the hydrophobic substrate-containing aggregate core and the catalyst-containing aqueous phase were then greatly favored, resulting in an increase in the catalytic performances.

Heterogeneous Synergistic Catalysis by a Palladium Complex and an Amine on a Silica Surface for Acceleration of the Tsuji–Trost Reaction

Heterogeneous Synergistic Catalysis by a Palladium Complex and an Amine on a Silica Surface for Acceleration of the Tsuji–Trost Reaction

ChemInform Abstract: Asymmetric Tsuji—Trost Substitution in 3‐Acetoxy‐1,3‐diphenylpropene under Phase‐Transfer Conditions.

P*-Chiral diamidophosphite ligand-assisted Pd-catalyzed Tsuji–Trost reaction between dimethyl malonate and prochiral 3-acetoxy-1,3-diphenylpropene in organic solvents using potassium carbonate as the base affords the substitution product in quantitative yields and with enantioselectivities up to 99% ee.

A highly sensitive fluorescence method reveals the presence of palladium in a cross-coupling reaction mixture not treated with transition metals

We previously reported a Suzuki–Miyaura coupling in dimethyl carbonate without adding additional transition metals. Here, we show an analysis of the reaction mixture that revealed the presence of palladium using a fluorogenic Tsuji–Trost reaction.

Regiodivergent Synthesis of Functionalized Indene Derivatives via Pt-Catalyzed Rautenstrauch Reaction of Propargyl Carbonates

A regiodivergent synthesis of functionalized indene derivatives from a Pt-catalyzed Rautenstrauch reaction of propargyl carbonate is described. A one-pot Rautenstrauch/Tsuji-Trost reaction delivering 2-indanones was realized efficiently using this methodology.

Detection of Trace Palladium in Flasks and Metal Reagents Using a Fluorogenic Tsuji–Trost Reaction

Detection of Trace Palladium in Flasks and Metal Reagents Using a Fluorogenic Tsuji–Trost Reaction

Asymmetric Tsuji–Trost substitution in 3-acetoxy-1,3-diphenylpropene under phase-transfer conditions

P*-Chiral diamidophosphite ligand-assisted Pd-catalyzed Tsuji–Trost reaction between dimethyl malonate and prochiral 3-acetoxy-1,3-diphenylpropene in organic solvents using potassium carbonate as the base affords the substitution product in quantitative yields and with enantioselectivities up to 99% ee.

ChemInform Abstract: Achieving Chemo‐, Regio‐, and Stereoselectivity in Palladium‐Catalyzed Reaction of γ‐Borylated Allylic Acetates.

AbstractStereocontrolled Tsuji—Trost reaction of various γ‐borylated allylic acetates is achieved using malonate, β‐ketoester, 3‐diketone, cyanoacetate or a cyclic ketoester as nucleophiles.

Design, synthesis and biological evaluation of peptidyl-vinylaminophosphonates as novel cysteine protease inhibitors

We report herein, design and synthesis of vinylaminophosphonates, a novel class of compounds as possible cysteine protease inhibitors. The synthesis of vinylaminophosphonates has been accomplished employing Tsuji–Trost reaction as a key step. The synthesized compounds were assayed against papain, a model cysteine protease and some of our synthesized compounds showed IC50 values in the range of 30–54μM thereby suggesting that these chemical entities thus could constitute an interesting template for the design of potential novel protease inhibitors.

Size- and shape-controlled palladium nanoparticles in a fluorometric Tsuji–Trost reaction

Palladium nanospheres of 2.4 and 3.8 nm diameter and nanocubes of 18 nm rib length were used to catalyze a fluorometric Tsuji–Trost reaction for the transformation of a phenyl allyl ether to a fluorescent phenol in the presence of triphenylphosphine, which was pivotal to the catalytic activity. Turnover frequencies calculated per defect atoms were found similar for all nanoparticles, indicating that these atoms are the active sites. However, kinetic studies combined with Pd leaching and transmission electron microscopy analyses in the presence of various reaction components showed Pd leaching via oxidative addition of a reactant, followed by nanoparticle growth depending on the PPh 3 concentration. The formation of largest particles was found for the fastest reaction with PPh 3/Pd molar ratio of 4, in the range from 0 to 9. This study shows the validity of the atomic dissolution mechanism in the reaction of interest.

ChemInform Abstract: Concise Synthesis of Tetrahydropyrans by a Tandem Oxa‐Michael/Tsuji—Trost Reaction.

AbstractA novel domino process is developed for the synthesis of polysubstituted title compounds.

An ordered hydrophobic P6mm mesoporous carbon with graphitic pore walls and its application in aqueous catalysis

A hydrophobic ordered mesoporous carbon with hexagonal arrays of rods was synthesized by a nanocasting process by using silica SBA-15 as a template and 2,3-dihydroxynaphthalene as a fused-aromatic carbon precursor. Impregnation of 2,3-dihydroxynaphthalene and its subsequent conversion into carbon occurred inside the mesopores of the silica template through a dehydration reaction between the surface silanols and hydroxyl groups of the carbon source and mild carbonization under inert atmosphere. After silica removal, X-ray scattering, transmission electron microscopy, pore size analysis and Raman spectroscopy showed that the resulting material was a negative replica of the silica template with a 2D-hexagonal P6mm ordered structure, possessing a large surface area (724 m 2 g −1), a monomodal pore size distribution (3.4 nm) and a relative hydrophobic surface with graphitic pore walls. These features give the system substantial advantages to play a beneficial role in aqueous organometallic catalysis. The material appeared to be an excellent mass transfer promoter to enhance the overall reaction rate of the palladium-catalyzed cleavage reaction of water-insoluble allylundecylcarbonate (Tsuji–Trost reaction).

Concise Synthesis of Tetrahydropyrans by a Tandem Oxa‐Michael/Tsuji–Trost Reaction

Concise Synthesis of Tetrahydropyrans by a Tandem Oxa‐Michael/Tsuji–Trost Reaction

ChemInform Abstract: Tsuji—Trost Allylations with Palladium Recovery by Phosphines/Pd(0)‐Triolefinic Macrocyclic Catalysts.

AbstractA Pd(0)—triolefinic azamacrocycle complex efficiently catalyzes the Tsuji—Trost reaction of allylic carbonate (I) with various N‐ and O‐nucleophiles.

ChemInform Abstract: Carboxylates as Pronucleophiles in the Phosphine-Catalyzed γ-Addition Reaction.

Abstract Carboxylates have been used as pronucleophiles in the phosphine-catalyzed γ-addition reaction to alkynes bearing electron-withdrawing groups (Trost's reaction) giving rise to functionalized allyl carboxylates.

ChemInform Abstract: Chiral, Non‐Racemic Diols, and α‐Amino Acid‐Derived β‐Amino Alcohols as Templates for Chiral Catalysts in the Tsuji—Trost Reaction.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Ditopic Cyclodextrin-Based Receptors: New Perspectives in Aqueous Organometallic Catalysis

The mass transfer properties of mono- and ditopic β-cyclodextrin-based receptors have been evaluated in a biphasic palladium-catalyzed Tsuji–Trost reaction and compared to one of the best mass-transfer promoters, namely the randomly methylated β-cyclodextrin. While monotopic receptors appeared to be poor mass-transfer promoters of long alkyl chain allyl carbonates or urethanes, cooperative effects have been evidenced with ditopic cyclodextrin-based receptors, opening new perspectives in aqueous organometallic catalysis.

ChemInform Abstract: Recyclable Heterogeneous Palladium Catalysts in Pure Water: Sustainable Developments in Suzuki, Heck, Sonogashira and Tsuji—Trost Reactions

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.