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Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions Open
Pd-catalyzed cross-coupling reactions that form C-N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of t…
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Electrochemical Arylation Reaction Open
Arylated products are found in various fields of chemistry and represent essential entities for many applications. Therefore, the formation of this structural feature represents a central issue of contemporary organic synthesis. By the act…
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C–H Activation: Toward Sustainability and Applications Open
Since the definition of the "12 Principles of Green Chemistry" more than 20 years ago, chemists have become increasingly mindful of the need to conserve natural resources and protect the environment through the judicious choice of syntheti…
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Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development Open
Photoredox catalysis has experienced a revitalized interest from the synthesis community during the past decade. For example, photoredox/Ni dual catalysis protocols have been developed to overcome several inherent limitations of palladium-…
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Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes Open
Two-for-one approach to photoredox In photoredox catalysis, an excited chromophore typically activates a single reactant either by oxidizing or reducing it. Ghosh et al. used a semiconductor catalyst to activate two reactants at once by qu…
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The Buchwald–Hartwig Amination After 25 Years Open
The Pd‐catalyzed coupling of aryl (pseudo)halides and amines is one of the most powerful approaches for the formation of C(sp 2 )−N bonds. The pioneering reports from Migita and subsequently Buchwald and Hartwig on the coupling of aminosta…
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Redox reactions of small organic molecules using ball milling and piezoelectric materials Open
Redox catalysis in a ball mill Mixing solid reactants in a ball mill is a promising means of avoiding the copious solvent waste associated with most chemical syntheses. Kubota et al. now report that adding a piezoelectric catalyst to the m…
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Aminoalkyl radicals as halogen-atom transfer agents for activation of alkyl and aryl halides Open
Amines as a gateway to alkyl radicals In recent years, photoredox catalysis driven by blue light has often been used to oxidize carbon centers adjacent to nitrogen. Constantin et al. now show that these aminoalkyl radicals can, in turn, co…
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Photosensitized, energy transfer-mediated organometallic catalysis through electronically excited nickel(II) Open
A nickel's worth of transferred energy Traditional organic photochemistry often relies on sensitizers, molecules that efficiently absorb light and then transfer the energy to other compounds to spur reactivity. Welin et al. leveraged this …
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Enantioselective Decarboxylative Arylation of α-Amino Acids via the Merger of Photoredox and Nickel Catalysis Open
An asymmetric decarboxylative Csp(3)-Csp(2) cross-coupling has been achieved via the synergistic merger of photoredox and nickel catalysis. This mild, operationally simple protocol transforms a wide variety of naturally abundant α-amino ac…
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Visible-Light-Promoted C–S Cross-Coupling via Intermolecular Charge Transfer Open
Disclosed is a mild, scalable, visible-light-promoted cross-coupling reaction between thiols and aryl halides for the construction of C-S bonds in the absence of both transition metal and photoredox catalysts. The scope of aryl halides and…
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A radical approach to the copper oxidative addition problem: Trifluoromethylation of bromoarenes Open
Arenes get a light boost onto copper Insertion of palladium into an aryl halide bond is the first step in numerous variants of cross-coupling chemistry used to make carbon-carbon bonds. Copper is an appealing alternative catalyst for such …
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Practical Ni-Catalyzed Aryl–Alkyl Cross-Coupling of Secondary Redox-Active Esters Open
A new transformation is presented that enables chemists to couple simple alkyl carboxylic acids with aryl zinc reagents under Ni-catalysis. The success of this reaction hinges on the unique use of redox-active esters that allow one to empl…
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Fe-Catalyzed C–C Bond Construction from Olefins via Radicals Open
This Article details the development of the iron-catalyzed conversion of olefins to radicals and their subsequent use in the construction of C-C bonds. Optimization of a reductive diene cyclization led to the development of an intermolecul…
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Decarboxylative Cross-Electrophile Coupling of <i>N</i>-Hydroxyphthalimide Esters with Aryl Iodides Open
A new method for the decarboxylative coupling of alkyl N-hydroxyphthalimide esters (NHP esters) with aryl iodides is presented. In contrast to previous studies that form alkyl radicals from carboxylic acid derivatives, no photocatalyst, li…
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Iodine(III) Reagents in Radical Chemistry Open
The chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as…
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Photoinduced Deaminative Borylation of Alkylamines Open
An operationally simple deaminative borylation reaction of primary alkylamines has been developed. The formation of electron-donor-acceptor complexes between N-alkylpyridinium salts and bis(catecholato)diboron enables photoinduced single-e…
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Potent Reductants via Electron-Primed Photoredox Catalysis: Unlocking Aryl Chlorides for Radical Coupling Open
We describe a new catalytic strategy to transcend the energetic limitations of visible light by electrochemically priming a photocatalyst prior to excitation. This new catalytic system is able to productively engage aryl chlorides with red…
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Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO<sub>2</sub> Open
The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic ac…
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Decarboxylative borylation Open
Swapping boron acids for carbon acids Carbon-bound boronic acids and their esters are widely used as coupling partners to make carbon-carbon bonds. More recently, these chemicals have garnered pharmaceutical interest in their own right. Li…
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Highly Efficient and Reversible Iodine Capture in Hexaphenylbenzene-Based Conjugated Microporous Polymers Open
The effective and safe capture and storage of radioactive iodine (129I or 131I) is of significant importance during nuclear waste storage and nuclear energy generation. Here we present detailed evidence of highly efficient and reversible i…
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Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications Open
C-N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industr…
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Catalytic, asymmetric difluorination of alkenes to generate difluoromethylated stereocenters Open
Difluoromethyl groups possess specific steric and electronic properties that invite their use as chemically inert surrogates of alcohols, thiols, and other polar functional groups important in a wide assortment of molecular recognition pro…
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Organocatalyzed Atom Transfer Radical Polymerization Using <i>N</i>-Aryl Phenoxazines as Photoredox Catalysts Open
N-Aryl phenoxazines have been synthesized and introduced as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization for the synthesis of well-defined polymers. Experiments confirmed quantum…
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Buchwald-Hartwig reaction: An overview Open
Pd-catalyzed amination reaction of aryl halides has attracted much attention in recent years. This review underscores selected important recent developments in the catalysis of one of the kind amination reaction so-called Buchwald-Hartwig …
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Base-Catalyzed Aryl-B(OH)<sub>2</sub> Protodeboronation Revisited: From Concerted Proton Transfer to Liberation of a Transient Aryl Anion Open
Pioneering studies by Kuivila, published more than 50 years ago, suggested ipso protonation of the boronate as the mechanism for base-catalyzed protodeboronation of arylboronic acids. However, the study was limited to UV spectrophotometric…
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“Inverse Drug Discovery” Strategy To Identify Proteins That Are Targeted by Latent Electrophiles As Exemplified by Aryl Fluorosulfates Open
Drug candidates are generally discovered using biochemical screens employing an isolated target protein or by utilizing cell-based phenotypic assays. Both noncovalent and covalent hits emerge from such endeavors. Herein, we exemplify an "I…
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Electrochemically Enabled, Nickel‐Catalyzed Amination Open
Along with amide bond formation, Suzuki cross‐coupling, and reductive amination, the Buchwald–Hartwig–Ullmann‐type amination of aryl halides stands as one of the most employed reactions in modern medicinal chemistry. The work herein demons…
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Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications Open
Cyclic (alkyl)- and (aryl)-(amino)carbenes (CAACs and CAArCs) are stronger σ-donors and π-acceptors than imidazol-2-ylidenes and imidazolidin-2-ylidenes, the well-known N-heterocyclic carbenes (NHCs). Consequently, they form strong bonds w…
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Dirhodium-catalyzed C-H arene amination using hydroxylamines Open
Primary and N -alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals, and functional materials, as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direc…