360 results match your criteria Acs Catalysis[Journal]


Cu-Catalyzed Hydroboration of Benzylidenecyclopropanes: Reaction Optimization, (Hetero)Aryl Scope, and Origins of Pathway Selectivity.

ACS Catal 2019 Dec 29;9(12):11130-11136. Epub 2019 Oct 29.

Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.

The copper-catalyzed hydroboration of benzylidenecyclopropanes, conveniently accessed in one step from readily available benzaldehydes, is reported. Under otherwise identical reaction conditions, two distinct phosphine ligands grant access to different products by either suppressing or promoting cyclopropane opening via β-carbon elimination. Computational studies provide insight into how the rigidity and steric environment of these different bis-phosphine ligands influence the relative activation energies of β-carbon elimination versus protodecupration from the key benzylcopper intermediate. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b03557DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7331956PMC
December 2019

B(CF)-Catalyzed Direct C3 Alkylation of Indoles and Oxindoles.

ACS Catal 2020 Apr 9;10(8):4835-4840. Epub 2020 Apr 9.

School of Chemistry, University of Leicester, Leicester, LE1 7RH, United Kingdom.

The direct C3 alkylation of indoles and oxindoles is a challenging transformation, and only a few direct methods exist. Utilizing the underexplored ability of triaryl boranes to mediate the heterolytic cleavage of α-nitrogen C-H bonds in amines, we have developed a catalytic approach for the direct C3 alkylation of a wide range of indoles and oxindoles using amine-based alkylating agents. We also employed this borane-catalyzed strategy in an alkylation-ring opening cascade. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c01141DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7311048PMC

Photocatalytic Deoxygenation of Sulfoxides Using Visible Light: Mechanistic Investigations and Synthetic Applications.

ACS Catal 2020 May 17;10(10):5814-5820. Epub 2020 Apr 17.

Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.

The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF)ppy)(dtbbpy)]PF or -Ir(ppy) is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00690DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7304878PMC

Mechanistic Understanding of the Heterogeneous, Rhodium-Cyclic (Alkyl)(Amino)Carbene-Catalyzed (Fluoro-)Arene Hydrogenation.

ACS Catal 2020 Jun 5;10(11):6309-6317. Epub 2020 May 5.

Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster, Germany.

Recently, chemoselective methods for the hydrogenation of fluorinated, silylated, and borylated arenes have been developed providing direct access to previously unattainable, valuable products. Herein, a comprehensive study on the employed rhodium-cyclic (alkyl)(amino)carbene (CAAC) catalyst precursor is disclosed. Mechanistic experiments, kinetic studies, and surface-spectroscopic methods revealed supported rhodium(0) nanoparticles (NP) as the active catalytic species. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c01074DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7295364PMC

In Situ X-ray Microscopy Reveals Particle Dynamics in a NiCo Dry Methane Reforming Catalyst under Operating Conditions.

ACS Catal 2020 Jun 1;10(11):6223-6230. Epub 2020 May 1.

Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, Mülheim an der Ruhr D-45470, Germany.

Herein, we report the synthesis of a γ-AlO-supported NiCo catalyst for dry methane reforming (DMR) and study the catalyst using in situ scanning transmission X-ray microscopy (STXM) during the reduction (activation step) and under reaction conditions. During the reduction process, the NiCo alloy particles undergo elemental segregation with Co migrating toward the center of the catalyst particles and Ni migrating to the outer surfaces. Under DMR conditions, the segregated structure is maintained, thus hinting at the importance of this structure to optimal catalytic functions. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b05517DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7295368PMC

The Dynamic Structure of Au(SR) Nanoclusters Supported on CeO upon Pretreatment and CO Oxidation.

ACS Catal 2020 Jun 8;10(11):6144-6148. Epub 2020 May 8.

Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/01, 1060 Vienna Austria.

Atomically precise thiolate protected Au nanoclusters Au(SCHPh) on CeO were used for in-situ (operando) extended X-ray absorption fine structure/diffuse reflectance infrared fourier transform spectroscopy and ex situ scanning transmission electron microscopy-high-angle annular dark-field imaging/X-ray photoelectron spectroscopy studies monitoring cluster structure changes induced by activation (ligand removal) and CO oxidation. Oxidative pretreatment at 150 °C "collapsed" the clusters' ligand shell, oxidizing the hydrocarbon backbone, but the S remaining on Au acted as poison. Oxidation at 250 °C produced bare Au surfaces by removing S which migrated to the support (forming Au-S), leading to highest activity. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c01621DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7295362PMC

Imaging the Heterogeneity of the Oxygen Evolution Reaction on Gold Electrodes Operando: Activity is Highly Local.

ACS Catal 2020 Jun 30;10(11):6084-6093. Epub 2020 Apr 30.

Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin, Germany.

Understanding the mechanism of the oxygen evolution reaction (OER), the oxidative half of electrolytic water splitting, has proven challenging. Perhaps the largest hurdle has been gaining experimental insight into the active site of the electrocatalyst used to facilitate this chemistry. Decades of study have clarified that a range of transition-metal oxides have particularly high catalytic activity for the OER. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c01177DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7295367PMC

Rewiring the "Push-Pull" Catalytic Machinery of a Heme Enzyme Using an Expanded Genetic Code.

ACS Catal 2020 Feb 29;10(4):2735-2746. Epub 2020 Jan 29.

Manchester Institute of Biotechnology, School of Chemistry, University of Manchester, 131 Princess Street, Manchester M1 7DN, U.K.

Nature employs a limited number of genetically encoded axial ligands to control diverse heme enzyme activities. Deciphering the functional significance of these ligands requires a quantitative understanding of how their electron-donating capabilities modulate the structures and reactivities of the iconic ferryl intermediates compounds I and II. However, probing these relationships experimentally has proven to be challenging as ligand substitutions accessible via conventional mutagenesis do not allow fine tuning of electron donation and typically abolish catalytic function. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b05129DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7273622PMC
February 2020

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis.

ACS Catal 2019 Sep 2;9(9):7626-7640. Epub 2019 Jul 2.

Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.

A weakly coordinating monodentate heteroaryl thioether directing group has been developed for use in Pd(II) catalysis to orchestrate key elementary steps in the catalytic cycle that require conformational flexibility in a manner that is difficult to accomplish with traditional strongly coordinating directing groups. This benzothiazole thioether, (BT)S, directing group can be used to promote oxidative Heck reactivity of internal alkenes providing a wide range of products in moderate to high yields. To demonstrate the broad applicability of this directing group, an arene C-H olefination method was also successfully developed. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b01471DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7295166PMC
September 2019

Switching on a Nontraditional Enzymatic Base - Deprotonation by Serine in the -Kaurene Synthase from .

ACS Catal 2019 Oct 27;9(10):8867-8871. Epub 2019 Aug 27.

Roy J. Carver Department of Biochemistry, Biophysics & Molecular Biology, Iowa State University, Ames, IA 50011, United States.

Terpene synthases often catalyze complex carbocation cascade reactions. It has been previously shown that single residue switches involving replacement of a key aliphatic residue with serine or threonine can "short-circuit" such reactions, presumed to act indirectly via dipole stabilization of intermediate carbocations. Here a similar switch was found in the structurally characterized -kaurene synthase from . Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02783DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7266162PMC
October 2019

Mechanism of Cobalt-Catalyzed Heterodimerization of Acrylates and 1,3-Dienes. A Potential Role of Cationic Cobalt(I) Intermediates.

ACS Catal 2020 Apr 3;10(7):4337-4348. Epub 2020 Mar 3.

151 W. Woodruff, Columbus, OH 43210 and the Department of Chemistry and Biochemistry, 100 W. 18th Avenue, Columbus, Ohio 43210, United States.

Coupling reactions of feedstock alkenes are promising, but few of these reactions are practiced industrially. Even though recent advances in the synthetic methodology have led to excellent regio- and enantioselectivies in the dimerization reactions between 1,3-dienes and acrylates, the efficiency as measured by the turnover numbers (TON) in the catalyst has remained modest. Through a combination of reaction progress kinetic analysis (RPKA) of a prototypical dimerization reaction, characterization of isolated low-valent cobalt catalyst precursors involved, several important details of the mechanism of this reaction have emerged. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b05455DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7250405PMC

Au/Pb Interface Allows the Methane Formation Pathway in Carbon Dioxide Electroreduction.

ACS Catal 2020 May 14;10(10):5681-5690. Epub 2020 Apr 14.

Department of Physical Chemistry and Materials Science, Interdisciplinary Excellence Centre, University of Szeged, Rerrich Square 1., Szeged H-6720, Hungary.

The electrochemical conversion of carbon dioxide (CO) to high-value chemicals is an attractive approach to create an artificial carbon cycle. Tuning the activity and product selectivity while maintaining long-term stability, however, remains a significant challenge. Here, we study a series of Au-Pb bimetallic electrocatalysts with different Au/Pb interfaces, generating carbon monoxide (CO), formic acid (HCOOH), and methane (CH) as CO reduction products. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00749DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7236132PMC

Selective Room-Temperature Hydrogenation of Amides to Amines and Alcohols Catalyzed by a Ruthenium Pincer Complex and Mechanistic Insight.

ACS Catal 2020 May 21;10(10):5511-5515. Epub 2020 Apr 21.

Department of Organic Chemistry, and Department of Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel.

We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports for this transformation, which use high temperatures (typically, 100-200 °C) and H pressures (10-100 bar), this system proceeds under extremely mild conditions (RT, 5-10 bar of H). The hydrogenation is catalyzed by well-defined ruthenium-PNNH pincer complexes (0. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c01406DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7236134PMC
May 2020
9.312 Impact Factor

Actinobacterial Coproheme Decarboxylases Use Histidine as a Distal Base to Promote Compound I Formation.

ACS Catal 2020 May 9;10(10):5405-5418. Epub 2020 Apr 9.

Department of Chemistry, Institute of Biochemistry, BOKU-University of Natural Resources and Life Sciences, A-1190 Vienna, Austria.

Coproheme decarboxylases (ChdCs) catalyze the final step in heme biosynthesis of monoderm and some diderm bacteria. In this reaction, coproheme is converted to heme via monovinyl monopropionate deuteroheme (MMD) in two consecutive decarboxylation steps. In Firmicutes decarboxylation of propionates 2 and 4 of coproheme depend on hydrogen peroxide and the presence of a catalytic tyrosine. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00411DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7235987PMC

Descriptor for Hydrogen Evolution Catalysts Based on the Bulk Band Structure Effect.

ACS Catal 2020 May 3;10(9):5042-5048. Epub 2020 Apr 3.

Max Planck Institute for Chemical Physics of Solids, 01187 Dresden, Germany.

The vital role of electrocatalysts in determining the efficiency of renewable energy conversion inspired the uncovering of the relation between the catalytic efficiency and electronic structure, in which the volcano-type plot based on adsorption energies and d-band model has achieved great success. At the same time, catalysts with nontrivial topological electronic structures have received considerable attention because of their robust topological surface states and high-mobility electrons, which favor the electrons transfer processes in the heterogeneous catalysis reactions. Under the guidance of this theory, excellent catalysts were reported among topological materials. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b05539DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7199788PMC

Facet-Dependent Selectivity of Cu Catalysts in Electrochemical CO Reduction at Commercially Viable Current Densities.

ACS Catal 2020 May 27;10(9):4854-4862. Epub 2020 Mar 27.

Laboratory of Nanochemistry for Energy, Institute of Chemical Sciences and Engineering, Ecole Politechnique Fédérale de Lausanne, Sion CH-1950, Switzerland.

Despite substantial progress in the electrochemical conversion of CO into value-added chemicals, the translation of fundamental studies into commercially relevant conditions requires additional efforts. Here, we study the catalytic properties of tailored Cu nanocatalysts under commercially relevant current densities in a gas-fed flow cell. We demonstrate that their facet-dependent selectivity is retained in this device configuration with the advantage of further suppressing hydrogen production and increasing the faradaic efficiencies toward the CO reduction products compared to a conventional H-cell. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00297DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7199425PMC

Substrate-Assisted Hydroxylation and -Demethylation in the Peroxidase-like Cytochrome P450 Enzyme CYP121.

ACS Catal 2020 Jan 20;10(2):1628-1639. Epub 2019 Dec 20.

University of Texas, San Antonio, Texas.

CYP121 is a P450 enzyme from that catalyzes a C-C coupling reaction between the two aromatic rings on its native substrate cyclo(l-Tyr-l-Tyr) (cYY) to form mycocyclosin, a necessary product for cell survival. Unlike the typical P450 enzymes for hydroxylation, CYP121 is believed to behave like a peroxidase and conduct radical-mediated C-C bond formation. Here, we probe whether the phenolic hydrogen of the substrate is the site of the postulated hydrogen atom abstraction for radical formation. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04596DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7207044PMC
January 2020

Comprehensive Insights into the Catalytic Mechanism of Middle East Respiratory Syndrome 3C-Like Protease and Severe Acute Respiratory Syndrome 3C-Like Protease.

ACS Catal 2020 28;10:5871-5890. Epub 2020 Apr 28.

State Key Laboratory of Medicinal Chemical Biology, College of Pharmacy and KLMDASR of Tianjin, Nankai University, No. 38 Tongyan Road, Haihe Education Park, Tianjin 300350, People's Republic of China.

Coronavirus 3C-like protease (3CL) is a highly conserved cysteine protease employing a catalytic dyad for its functions. 3CL is essential to the viral life cycle and, therefore, is an attractive target for developing antiviral agents. However, the detailed catalytic mechanism of coronavirus 3CL remains largely unknown. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00110DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7202269PMC

Protein Conformational Change Is Essential for Reductive Activation of Lytic Polysaccharide Monooxygenase by Cellobiose Dehydrogenase.

ACS Catal 2020 May 30;10(9):4842-4853. Epub 2020 Mar 30.

Manchester Institute of Biotechnology, The University of Manchester, M1 7DN Manchester, United Kingdom.

Large-scale protein domain dynamics and electron transfer are often associated. However, as protein motions span a broad range of time and length scales, it is often challenging to identify and thus link functionally relevant dynamic changes to electron transfer in proteins. It is hypothesized that large-scale domain motions direct electrons through a FAD and a heme cofactor of the fungal cellobiose dehydrogenase (CDH) enzymes to the type-II copper center (T2Cu) of the polysaccharide-degrading lytic polysaccharide monooxygenases (LPMOs). Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00754DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7199207PMC

Dynamics of a Key Conformational Transition in the Mechanism of Peroxiredoxin Sulfinylation.

ACS Catal 2020 Mar 31;10(5):3326-3339. Epub 2020 Jan 31.

IMoPA, Université de Lorraine, CNRS, Biopole, Campus Biologie Sante', F-54000 Nancy, France.

Peroxiredoxins from the Prx1 subfamily (Prx) are moonlighting peroxidases that operate in peroxide signaling and are regulated by sulfinylation. Prxs offer a major model of protein-thiol oxidative modification. They react with HO to form a sulfenic acid intermediate that either engages into a disulfide bond, committing the enzyme into its peroxidase cycle, or again reacts with peroxide to produce a sulfinic acid that inactivates the enzyme. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04471DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7189429PMC

Enantioselective Electroreductive Coupling of Alkenyl and Benzyl Halides via Nickel Catalysis.

ACS Catal 2019 Aug 25;9(8):6751-6754. Epub 2019 Jul 25.

The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.

An electrochemically-driven enantioselective nickel-catalyzed reductive cross-coupling of alkenyl bromides and benzyl chlorides is reported. The reaction forms products bearing allylic stereogenic centers with good enantioselectivity under mild conditions in an undivided cell. Electrochemical activation and turnover of the catalyst mitigate issues posed by metal powder reductants. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b01785DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7190267PMC

Biocatalytic Synthesis of Moclobemide Using the Amide Bond Synthetase McbA Coupled with an ATP Recycling System.

ACS Catal 2020 Apr 30;10(8):4659-4663. Epub 2020 Mar 30.

Department of Chemistry, University of York, YO10 5DD York, United Kingdom.

The biocatalytic synthesis of amides from carboxylic acids and primary amines in aqueous media can be achieved using the ATP-dependent amide bond synthetase McbA, via an adenylate intermediate, using only 1.5 equiv of the amine nucleophile. Following earlier studies that characterized the broad carboxylic acid specificity of McbA, we now show that, in addition to the natural amine substrate 2-phenylethylamine, a range of simple aliphatic amines, including methylamine, butylamine, and hexylamine, and propargylamine are coupled efficiently to the native carboxylic acid substrate 1-acetyl-9-β-carboline-3-carboxylic acid by the enzyme, to give amide products with up to >99% conversion. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00929DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7171872PMC

Solar-Enhanced Plasma-Catalytic Oxidation of Toluene over a Bifunctional Graphene Fin Foam Decorated with Nanofin-like MnO.

ACS Catal 2020 Apr 25;10(7):4420-4432. Epub 2020 Mar 25.

Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool L69 3GJ, U.K.

In this work, we propose a hybrid and unique process combining solar irradiation and post-plasma catalysis (PPC) for the effective oxidation of toluene over a highly active and stable MnO/GFF (bifunctional graphene fin foam) catalyst. The bifunctional GFF, serving as both the catalyst support and light absorber, is decorated with MnO nanofins, forming a hierarchical fin-on-fin structure. The results show that the MnO/GFF catalyst can effectively capture and convert renewable solar energy into heat (absorption of >95%), leading to a temperature rise (55. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04844DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7147263PMC

Solid-State Molecular Organometallic Catalysis in Gas/Solid Flow (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure 1-Butene Isomerization.

ACS Catal 2020 Feb 6;10(3):1984-1992. Epub 2020 Jan 6.

Department of Chemistry, Chemistry Research Laboratories, University of Oxford, Oxford OX1 3TA, United Kingdom.

The use of solid-state molecular organometallic chemistry (SMOM-chem) to promote the efficient double bond isomerization of 1-butene to 2-butenes under flow-reactor conditions is reported. Single crystalline catalysts based upon the σ-alkane complexes [Rh(RPCHCHPR)(ηη-NBA)][BAr] (R = Cy, Bu; NBA = norbornane; Ar = 3,5-(CF)CH) are prepared by hydrogenation of a norbornadiene precursor. For the Bu-substituted system this results in the loss of long-range order, which can be re-established by addition of 1-butene to the material to form a mixture of [Rh(BuPCHCHPBu)(-2-butene)][BAr] and [Rh(BuPCHCHPBu)(1-butene)][BAr], in an order/disorder/order phase change. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b03727DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7147255PMC
February 2020

PCET-Enabled Olefin Hydroamidation Reactions with -Alkyl Amides.

ACS Catal 2019 May 17;9(5):4502-4507. Epub 2019 Apr 17.

Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.

Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in -alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b00966DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7156045PMC

The Influence of the Ligand in the Iridium Mediated Electrocatalyic Water Oxidation.

ACS Catal 2020 Apr 17;10(7):4398-4410. Epub 2020 Mar 17.

Leiden Institute of Chemistry, Leiden University, 2300 RA Leiden, The Netherlands.

Electrochemical water oxidation is the bottleneck of electrolyzers as even the best catalysts, iridium and ruthenium oxides, have to operate at significant overpotentials. Previously, the position of a hydroxyl on a series of hydroxylpicolinate ligands was found to significantly influence the activity of molecular iridium catalysts in sacrificial oxidant driven water oxidation. In this study, these catalysts were tested under electrochemical conditions and benchmarked to several other known molecular iridium catalysts under the exact same conditions. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00531DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7137537PMC

Crystal Structure of the Ergothioneine Sulfoxide Synthase from and Structure-Guided Engineering To Modulate Its Substrate Selectivity.

ACS Catal 2019 Aug 2;9(8):6955-6961. Epub 2019 Jul 2.

Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, United States.

Ergothioneine is a thiohistidine derivative with potential benefits on many aging-related diseases. The central step of aerobic ergothioneine biosynthesis is the oxidative C-S bond formation reaction catalyzed by mononuclear nonheme iron sulfoxide synthases (EgtB and Egt1). Thus far, only the EgtB (EgtB ) crystal structure is available, while the structural information for the more industrially attractive Egt1 enzyme is not. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02054DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7133768PMC

Stereoselective Cyclopropanation of Electron-Deficient Olefins with a Cofactor Redesigned Carbene Transferase Featuring Radical Reactivity.

ACS Catal 2019 Oct 5;9(10):9683-9697. Epub 2019 Sep 5.

Department of Chemistry, University of Rochester, Rochester, NY 14627, United States.

Engineered myoglobins and other hemoproteins have recently emerged as promising catalysts for asymmetric olefin cyclopropanation reactions via carbene transfer chemistry. Despite this progress, the transformation of electron-poor alkenes has proven very challenging using these systems. Here, we describe the design of a myoglobin-based carbene transferase incorporating a non-native iron-porphyrin cofactor and axial ligand, as an efficient catalyst for the asymmetric cyclopropanation of electron-deficient alkenes. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02272DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7111255PMC
October 2019

Highly Stereoselective Synthesis of Fused Cyclopropane-γ-Lactams via Biocatalytic Iron-Catalyzed Intramolecular Cyclopropanation.

ACS Catal 2020 Feb 14;10(3):2308-2313. Epub 2020 Jan 14.

Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, NY 14627, United States.

We report the development of an iron-based biocatalytic strategy for the asymmetric synthesis of fused cyclopropane-γ-lactams, which are key structural motifs found in synthetic drugs and bioactive natural products. Using a combination of mutational landscape and iterative site-saturation mutagenesis, sperm whale myoglobin was evolved into a biocatalyst capable of promoting the cyclization of a diverse range of allyl diazoacetamide substrates into the corresponding bicyclic lactams in high yields and with high enantioselectivity (up to 99% ). These biocatalytic transformations can be performed in whole cells and could be leveraged to enable the efficient (chemo)enzymatic construction of chiral cyclopropane-γ-lactams as well as β-cyclopropyl amines and cyclopropane-fused pyrrolidines, as valuable building blocks and synthons for medicinal chemistry and natural product synthesis. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b05383DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7111458PMC
February 2020

Highly Effective Propane Dehydrogenation Using Ga-Rh Supported Catalytically Active Liquid Metal Solutions.

ACS Catal 2019 Oct 6;9(10):9499-9507. Epub 2019 Sep 6.

Lehrstuhl für Chemische Reaktionstechnik (CRT), Lehrstuhl für Theoretische Chemie, Lehrstuhl für Physikalische Chemie II, and Lehrstuhl für Katalytische Grenzflächenforschung, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstr. 3, 91058 Erlangen, Germany.

Our contribution demonstrates that rhodium, an element that has barely been reported as an active metal for selective dehydrogenation of alkanes becomes a very active, selective, and robust dehydrogenation catalyst when exposed to propane in the form of single atoms at the interface of a solid-supported, highly dynamic liquid Ga-Rh mixture. We demonstrate that the transition to a fully liquid supported alloy droplet at Ga/Rh ratios above 80, results in a drastic increase in catalyst activity with high propylene selectivity. The combining results from catalytic studies, X-ray photoelectron spectroscopy, IR-spectroscopy under reaction conditions, microscopy, and density-functional theory calculations, we obtained a comprehensive microscopy picture of the working principle of the Ga-Rh supported catalytically active liquid metal solution. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02459DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7088128PMC
October 2019

Ag/Pd Cocatalyzed Direct Arylation of Fluoroarene Derivatives with Aryl Bromides.

ACS Catal 2020 Feb 9;10(3):2100-2107. Epub 2020 Jan 9.

School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.

Diverse C-H functionalizations catalyzed by Pd employ Ag(I) salts added as halide abstractors or oxidants. Recent reports have shown that Ag can also perform the crucial C-H activation step in several of these functionalizations. However, all of these processes are limited by the wasteful requirement for (super)stoichiometric Ag(I) salts. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b05334DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7079724PMC
February 2020

H· Transfer-Initiated Synthesis of -Lactams: Interpretation of Cycloisomerization and Hydrogenation Ratios.

ACS Catal 2019 Nov 9;9(11):10294-10298. Epub 2019 Oct 9.

Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, United States.

A cobaloxime/H system used to synthesize valuable -lactams from acrylamide molecules is described. In addition to cycloisomerized lactams, linear hydrogenated products were also observed. The amounts of the hydrogenation product were observed to correlate with the bulk of the substituent on the acrylamide nitrogen. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b03678DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7082086PMC
November 2019

Enantioselective Aldol Addition of Acetaldehyde to Aromatic Aldehydes Catalyzed by Proline-Based Carboligases.

ACS Catal 2020 Feb 28;10(4):2522-2527. Epub 2020 Jan 28.

Department of Chemical and Pharmaceutical Biology, Groningen Research Institute of Pharmacy, University of Groningen, Antonius Deusinglaan 1, 9713 AV Groningen, The Netherlands.

Aromatic β-hydroxyaldehydes, 1,3-diols, and α,β-unsaturated aldehydes are valuable precursors to biologically active natural products and drug molecules. Herein we report the biocatalytic aldol condensation of acetaldehyde with various aromatic aldehydes to give a number of aromatic α,β-unsaturated aldehydes using a previously engineered variant of 4-oxalocrotonate tautomerase [4-OT(M45T/F50A)] as carboligase. Moreover, an efficient one-pot two-step chemoenzymatic route toward chiral aromatic 1,3-diols has been developed. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.0c00039DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7045556PMC
February 2020
9.312 Impact Factor

Vanadium-Catalyzed Selective Oxidative Homocoupling of Alkenyl Phenols to Synthesize Lignan Analogs.

ACS Catal 2019 Dec 23;9(12):11067-11073. Epub 2019 Oct 23.

Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

The oxidative homocoupling of -alkenyl phenols and subsequent trapping of the resulting quinone methide with a variety of oxygen and nitrogen nucleophiles was achieved. Both β-β and β-O coupling isomers can be synthesized via either C-C coupling and two nucleophilic additions of one water molecule (β-β isomer) or C-O coupling followed by one nucleophilic addition of a water molecule (β-O isomer), respectively. Selectivity between these outcomes was achieved by leveraging understanding of the mechanism. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02608DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7043397PMC
December 2019

Iron-Catalyzed Borrowing Hydrogen β-(sp)-Methylation of Alcohols.

ACS Catal 2019 Sep 21;9(9):8575-8580. Epub 2019 Aug 21.

Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, U.K.

Herein we report the iron-catalyzed (sp)-methylation of primary alcohols using methanol as a C1 building block. This borrowing hydrogen approach employs a well-defined bench-stable (cyclopentadienone)iron(0) carbonyl complex as precatalyst (5 mol %) and enables a diverse selection of substituted 2-arylethanols to undergo (sp)-methylation in good isolated yields (24 examples, 65% average yield). Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02461DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011770PMC
September 2019

Tunable Covalent Triazine-Based Frameworks (CTF-0) for Visible-Light-Driven Hydrogen and Oxygen Generation from Water Splitting.

ACS Catal 2019 Sep 16;9(9):7697-7707. Epub 2019 Jul 16.

Department of Chemical Engineering, University College London, Torrington Place, London, WC1E 7JE, United Kingdom.

Covalent triazine-based frameworks (CTFs), a group of semiconductive polymers, have been identified for photocatalytic water splitting recently. Their adjustable band gap and facile processing offer great potential for discovery and development. Here, we present a series of CTF-0 materials fabricated by two different approaches, a microwave-assisted synthesis and an ionothermal method, for water splitting driven by visible-light irradiation. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02195DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011733PMC
September 2019

Retooling Asymmetric Conjugate Additions for Sterically Demanding Substrates with an Iterative Data-Driven Approach.

ACS Catal 2019 Aug 2;9(8):7179-7187. Epub 2019 Jul 2.

Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, United Kingdom.

The development of catalytic enantioselective methods is routinely carried out using easily accessible and prototypical substrates. This approach to reaction development often yields asymmetric methods that perform poorly using substrates that are sterically or electronically dissimilar to those used during the reaction optimization campaign. Consequently, expanding the scope of previously optimized catalytic asymmetric reactions to include more challenging substrates is decidedly nontrivial. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b01814DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011729PMC

Impact of Nanoparticle-Support Interactions in CoO/AlO Catalysts for the Preferential Oxidation of Carbon Monoxide.

ACS Catal 2019 Aug 28;9(8):7166-7178. Epub 2019 Jun 28.

Catalysis Institute and cchange (DST-NRF Centre of Excellence in Catalysis), Department of Chemical Engineering, University of Cape Town, Rondebosch 7701, South Africa.

Different supporting procedures were followed to alter the nanoparticle-support interactions (NPSI) in two CoO/AlO catalysts, prepared using the reverse micelle technique. The catalysts were tested in the dry preferential oxidation of carbon monoxide (CO-PrOx) while their phase stability was monitored using four complementary in situ techniques, viz., magnet-based characterization, PXRD, and combined XAS/DRIFTS, as well as quasi in situ XPS, respectively. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b00685DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011734PMC

Catalytic Asymmetric C-H Arylation of (η-Arene)Chromium Complexes: Facile Access to Planar-Chiral Phosphines.

ACS Catal 2019 Jun 25;9(6):5268-5278. Epub 2019 Apr 25.

School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom.

A catalytic asymmetric direct C-H arylation of (η-arene)chromium complexes to obtain planar-chiral compounds is reported. The use of the hemilabile ligand H-BINAP(O) is key to providing high enantioselectivity in this transformation. We show that this methodology opens the door to the synthesis of a variety of planar-chiral chromium derivatives which can be easily transformed into planar chiral mono- or diphosphines. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b00918DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011738PMC

Plasma-Enhanced Catalytic Synthesis of Ammonia over a Ni/AlO Catalyst at Near-Room Temperature: Insights into the Importance of the Catalyst Surface on the Reaction Mechanism.

ACS Catal 2019 Dec 18;9(12):10780-10793. Epub 2019 Oct 18.

Department of Electrical Engineering and Electronics, University of Liverpool, Liverpool L69 3GJ, United Kingdom.

A better fundamental understanding of the plasma-catalyst interaction and the reaction mechanism is vital for optimizing the design of catalysts for ammonia synthesis by plasma-catalysis. In this work, we report on a hybrid plasma-enhanced catalytic process for the synthesis of ammonia directly from N and H over transition metal catalysts (M/AlO, M = Fe, Ni, Cu) at near room temperature (∼35 °C) and atmospheric pressure. Reactions were conducted in a specially designed coaxial dielectric barrier discharge (DBD) plasma reactor using water as a ground electrode, which could cool and maintain the reaction at near-room temperature. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02538DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011700PMC
December 2019

Inverse Opal CuCrO Photocathodes for H Production Using Organic Dyes and a Molecular Ni Catalyst.

ACS Catal 2019 Oct 9;9(10):9530-9538. Epub 2019 Sep 9.

Christian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.

Dye-sensitized photoelectrochemical (DSPEC) cells are an emerging approach to producing solar fuels. The recent development of delafossite CuCrO as a p-type semiconductor has enabled H generation through the coassembly of catalyst and dye components. Here, we present a CuCrO electrode based on a high-surface-area inverse opal (IO) architecture with benchmark performance in DSPEC H generation. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02984DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011728PMC
October 2019

Influence of Promotion on the Growth of Anchored Colloidal Iron Oxide Nanoparticles during Synthesis Gas Conversion.

ACS Catal 2020 Feb 8;10(3):1913-1922. Epub 2020 Jan 8.

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.

Using colloidal iron oxide nanoparticles with organic ligands, anchored in a separate step from the supports, has been shown to be beneficial to obtain homogeneously distributed metal particles with a narrow size distribution. Literature indicates that promoting these particles with sodium and sulfur creates an active Fischer-Tropsch catalyst to produce olefins, while further adding an H-ZSM-5 zeolite is an effective way to obtain aromatics. This research focused on the promotion of iron oxide colloids with sodium and sulfur using an inorganic ligand exchange followed by the attachment to H-ZSM-5 zeolite crystals. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04380DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7011703PMC
February 2020

Unexpected Roles of a Tether Harboring a Tyrosine Gatekeeper Residue in Modular Nitrite Reductase Catalysis.

ACS Catal 2019 Jul 29;9(7):6087-6099. Epub 2019 May 29.

Manchester Institute of Biotechnology and School of Chemistry, Faculty of Science and Engineering, The University of Manchester, 131 Princess Street, Manchester M1 7DN, United Kingdom.

It is generally assumed that tethering enhances rates of electron harvesting and delivery to active sites in multidomain enzymes by proximity and sampling mechanisms. Here, we explore this idea in a tethered 3-domain, trimeric copper-containing nitrite reductase. By reverse engineering, we find that tethering does not enhance the rate of electron delivery from its pendant cytochrome to the catalytic copper-containing core. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b01266DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7007197PMC

Molecular Mechanisms of Oxygen Activation and Hydrogen Peroxide Formation in Lytic Polysaccharide Monooxygenases.

ACS Catal 2019 Jun 22;9(6):4958-4969. Epub 2019 Apr 22.

Departament de Química Inorgànica i Orgànica & IQTCUB, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.

Lytic polysaccharide monooxygenases (LPMOs) are copper-dependent enzymes for the degradation of recalcitrant polysaccharides such as chitin and cellulose. Unlike classical hydrolytic enzymes (cellulases), LPMOs catalyze the cleavage of the glycosidic bond via an oxidative mechanism using oxygen and a reductant. The full enzymatic molecular mechanisms, starting from the initial electron transfer from a reductant to oxygen activation and hydrogen peroxide formation, are not yet understood. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b00778DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7007194PMC

Loss of Hyperconjugative Effects Drives Hydride Transfer during Dihydrofolate Reductase Catalysis.

ACS Catal 2019 Nov 23;9(11):10343-10349. Epub 2019 Sep 23.

School of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, United Kingdom.

Hydride transfer is widespread in nature and has an essential role in applied research. However, the mechanisms of how this transformation occurs in living organisms remain a matter of vigorous debate. Here, we examined dihydrofolate reductase (DHFR), an enzyme that catalyzes hydride from C4' of NADPH to C6 of 7,8-dihydrofolate (HF). Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02839DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC7007191PMC
November 2019

Rational Engineered C-Acyltransferase Transforms Sterically Demanding Acyl Donors.

ACS Catal 2020 Jan 27;10(2):1094-1101. Epub 2019 Dec 27.

Institute of Chemistry, University of Graz, NAWI Graz, BioTechMed Graz, Heinrichstrasse 28, 8010 Graz, Austria.

The biocatalytic Friedel-Crafts acylation has been identified recently for the acetylation of resorcinol using activated acetic acid esters for the synthesis of acetophenone derivatives catalyzed by an acyltransferase. Because the wild-type enzyme is limited to acetic and propionic derivatives as the substrate, variants were designed to extend the substrate scope of this enzyme. By rational protein engineering, the key residue in the active site was identified which can be replaced to allow binding of bulkier acyl moieties. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04617DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6996649PMC
January 2020

Unraveling the High Activity of Ylide-Functionalized Phosphines in Palladium-Catalyzed Amination Reactions: A Comparative Study with JohnPhos and PBu.

ACS Catal 2020 Jan 11;10(2):999-1009. Epub 2019 Dec 11.

Chair of Inorganic Chemistry II, Faculty of Chemistry and Biochemistry, Ruhr University Bochum, Universitätsstrasse 150, 44780 Bochum, Germany.

Comprehensive mechanistic insights into the activity of different catalysts based on different ligands are important for further ligand design and catalyst improvement. Herein, we report a combined computational and experimental study on the mechanism and catalytic activity of the ylide-substituted phosphine CyP-C(Me)PCy (keYPhos, ) in C-N coupling reactions including a comparison with the established and often-applied phosphines JohnPhos () and P(Bu) (). Density functional theory (DFT) calculations together with the possible isolation of several intermediates within the catalytic cycle demonstrate that readily forms low-coordinated palladium complexes [such as ], which easily undergo oxidative addition and subsequent amine coordination as well as reductive elimination. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04666DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6996648PMC
January 2020

Catalysis by the Non-Heme Iron(II) Histone Demethylase PHF8 Involves Iron Center Rearrangement and Conformational Modulation of Substrate Orientation.

ACS Catal 2020 Jan 11;10(2):1195-1209. Epub 2019 Dec 11.

Department of Chemistry, Michigan Technological University, Houghton, Michigan 49931, United States.

PHF8 (KDM7B) is a human non-heme 2-oxoglutarate (2OG) JmjC domain oxygenase that catalyzes the demethylation of the di/mono-N-methylated K9 residue of histone H3. Altered PHF8 activity is linked to genetic diseases and cancer; thus, it is an interesting target for epigenetic modulation. We describe the use of combined quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations to explore the mechanism of PHF8, including dioxygen activation, 2OG binding modes, and substrate demethylation steps. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b04907DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6970271PMC
January 2020

Engineering Chemoselectivity in Hemoprotein-Catalyzed Indole Amidation.

ACS Catal 2019 Sep 7;9(9):8271-8275. Epub 2019 Aug 7.

Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.

Here we report a cytochrome P450 variant that catalyzes C-amidation of 1-methylindoles with tosyl azide via nitrene transfer. Before evolutionary optimization the enzyme exhibited two undesired side reactivities resulting in reduction of the putative iron-nitrenoid intermediate or cycloaddition between the two substrates to form triazole products. We speculated that triazole formation was a promiscuous cycloaddition activity of the P450 heme domain, while sulfonamide formation likely arose from surplus electron transfer from the reductase domain. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b02508DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6959474PMC
September 2019
9.312 Impact Factor

Monophosphine Ligands Promote Pd-Catalyzed C-S Cross-Coupling Reactions at Room Temperature with Soluble Bases.

ACS Catal 2019 Jul 21;9(7):6461-6466. Epub 2019 Jun 21.

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.

The Pd-catalyzed cross-coupling of thiols with aromatic electrophiles is a reliable method for the synthesis of aryl thioethers, which are important compounds for pharmaceutical and agricultural applications. Since thiols and thiolates strongly bind late transition metals, previous research has focused on catalysts supported by chelating, bisphosphine ligands, which were considered less likely to be displaced during the course of the reaction. We show that by using monophosphine ligands instead, more effective catalysis can be achieved. Read More

View Article

Download full-text PDF

Source
http://dx.doi.org/10.1021/acscatal.9b01913DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6953912PMC