Bill Morandi

• Max-Planck-Institut für Kohlenforschung

Facile derivatization of biologically active compounds without prefunctionalization expands the chemical space and accelerates the discovery of new molecules. Atom swap reactions have recently emerged as powerful molecular editing tools, yet such reactions remain rare. Herein, we describe a convenient, chemodivergent protocol to perform a net C-to-...

Reductive elimination is the key bond-forming elementary step in many transition metal catalyzed reactions relevant to the synthesis of pharmaceuticals, materials and fine chemicals. Metal electronics, ancillary ligand sterics and metal complex coordination number have been identified as the primary factors which affect the rate of reductive elimin...

Metathesis and reversible catalytic reactions are fundamentally intriguing and powerful tools in modern synthetic chemistry. While most reversible catalytic reactions are predicated on breaking and forming reactive functional groups, the ability to leverage the C–H bond as a functional group into metathesis reactions has proved to be exceptionally...

The synthesis of nitrogen-containing molecules through carbon–nitrogen (C–N) bond formation is critical for the discovery and preparation of medicines, agrochemicals, and materials. Here, we report the direct insertion of a nitrogen atom into unactivated carbon-carbon double bonds to access aza-allenium intermediates, which can be converted either...

Herein, we demonstrate that ligand design enables the direct addition of acid chlorides across alkynes in a single step with complete atom economy to afford α,β-unsaturated acid chloride products. This carbochlorocarbonylation reaction, which proceeds through formal cleavage and reassembly of C–COCl bonds, was developed and explored for a range of...

In industry, the two important nitrile starting materials, adiponitrile and 2‐methylglutaronitrile, are primarily manufactured through the well‐known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency a...

In industry, the two important nitrile starting materials, adiponitrile and 2‐methylglutaronitrile, are primarily manufactured through the well‐known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency a...

Cross-electrophile coupling reactions have evolved into a major strategy for rapidly assembling important organic molecules¹. Two readily accessible electrophiles are coupled to form new C–C bonds, providing a key advantage over traditional cross-coupling strategies that require the preformation of reactive organometallic species. Yet, the formatio...

A base-promoted olefination reaction between alkylphosphonium salts and activated alkyl halides has been developed. The products were obtained in excellent E-selectivity. In contrast to most other olefination reactions of phosphonium salts, the reaction yields triphenylphosphine as the main by-product, which can be directly reused in the formation...

The power and ability of catalysis to build multiple C−C bonds in a single step has had a transformative impact on organic synthesis. While the reactivity of organohalides with metal catalysts is widely appreciated, the related and more intricate reactivity of acid chlorides is less so, despite their use as common reagents in synthesis. Here, we re...

Hydrogen atom transfer (HAT) from a metal-hydride is a reliable and powerful method for functionalizing unsaturated C–C bonds in organic synthesis. Cobalt hydrides (Co–H) have garnered significant attention in this field, where the weak Co–H bonds are most commonly generated in a catalytic fashion through a mixture of stoichiometric amounts of pero...

The ability to selectively edit organic molecules at the atomic level has the potential to streamline lead discovery and optimization in the pharmaceutical and agrochemical industry. While numerous atom insertion and deletion reactions have recently been reported, examples of single atom swaps remain scarce due to the challenge of orchestrating the...

Herein we report the development of an oxidative amination process for the streamlined synthesis of pyridones from cyclopentenones. Cyclopentenone building blocks can undergo in situ silyl enol ether formation, followed by the introduction of a nitrogen atom into the carbon skeleton with successive aromatisation to yield pyridones. The reaction seq...

We report the utilisation of an iodine(III) reagent to access α,β-unsaturated carbonyls from the corresponding silyl enol ethers of ketones and aldehydes, and from enol phosphates of lactones and lactams....

Herein we report the development of an oxidative amination process for the streamlined synthesis of pyridones from cyclopentenones. Cyclopentenone building blocks can undergo in situ silyl enol ether formation, followed by the introduction of a nitrogen atom into the carbon skeleton with successive aromatisation to yield pyridones. The reaction seq...

The synthesis of nitrogen-containing molecules through C–N bond formation is critical for the discovery and preparation of medicines, agrochemicals and materials. Traditional synthetic methods using alkenes as ubiquitous substrates leverage the reactivity of the C(sp2)–C(sp2) π bond for C–N bond formation. In contrast, methods that can form C–N bon...

The development of divergent methods to expedite structure–activity relationship studies is crucial to streamline discovery processes. We developed a rare example of regiodivergent ring expansion to access two regioisomers from a common starting material. To enable this regiodivergence, we identified two distinct reaction conditions for transformin...

Hydrogen atom transfer (HAT) from a metal-hydride is a reliable and powerful method for functionalizing unsaturated C–C bonds in organic synthesis. Cobalt hydrides (Co–H) have garnered significant attention in this field, where the weak Co–H bonds are most commonly generated in a catalytic fashion through a mixture of stoichiometric amounts of pero...

Carbon–carbon (C–C) bonds are ubiquitous but are among the least reactive bonds in organic chemistry. Recently, catalytic approaches to activate C–C bonds by transition metals have demonstrated the synthetic potential of directly reorganizing the skeleton of small molecules. However, these approaches are usually restricted to strained molecules or...

Classical metalation reactions such as the metal-halogen exchange have had a transformative impact on organic synthesis owing to their broad applicability in building carbon-carbon bonds from carbon-halogen bonds. Extending the metal-halogen exchange logic to a metal-carbon exchange would enable the direct modification of carbon frameworks with new...

Herein, a method for the isomerization of ketones in a manner akin to the chain-walking reaction of alkenes is described. Widely available and inexpensive pyrrolidine and elemental sulfur are deployed as catalysts to achieve this reversible transformation. Key to the utility of this approach was the elucidation of a stereochemical model to determin...

Given the prevalence of molecules containing nitro groups in organic synthesis, innovative methods to expand the reactivity of this functional group are of interest in both industrial and academic settings. In this report, a metal‐free intramolecular benzylic sp³ C−H amination is disclosed using aryl nitro compounds as aryl nitrene precursors. Orga...

The implementation of HCN-free transfer hydrocyanation reactions on laboratory scales has recently been achieved by using HCN donor reagents under nickel- and Lewis acid co-catalysis. More recently, malononitrile-based HCN donor reagents were shown to undergo the C(sp3)-CN bond activation by the nickel catalyst in the absence of Lewis acids. Howeve...

Cross-electrophile coupling reactions have evolved into a major strategy for rapidly assembling important molecules, yet challenges remain for the formation of C(sp3)–C(sp3) bonds that form the core of nearly all organic compounds. Herein, we report a distinct, transition metal-free platform to form such bonds without the need for activating or sta...

Oxygenated molecules are omnipresent in natural as well as artificial settings making the redox transformation of the present C–O bonds a central tool for their processing. However, the required (super)stoichiometric redox agents which traditionally include highly reactive and hazardous reagents pose multiple practical challenges including process...

We report the synthesis of coordinatively unsaturated cationic rhodium complexes bearing the sterically encumbered electron‐rich NHC ligand IPr*OMe. The COD (1,5‐cyclooctadiene) complex [Rh(IPr*OMe)(COD)]BF4 adopts a tilted, pseudo‐square planar coordination geometry, where bonding to the ipso‐carbon of the NHC aryl substituent was observed in the...

A broadly applicable and efficient method for the synthesis of N-alkyliminophosphoranes from phosphines that does not use potentially hazardous alkyl azides is reported. Under iron catalysis, a hydroxylamine-derived triflic acid salt oxidizes phosphines to a wide range of iminophosphorane triflic acid salts. Diphosphines afford phosphine-iminophosp...

We report a convenient protocol for a nitrogen atom insertion into indenes to afford isoquinolines. The reaction uses a combination of commercially available phenyliodine(iii) diacetate (PIDA) and ammonium carbamate as the nitrogen source to furnish a wide range of isoquinolines. Various substitution patterns and commonly used functional groups are...

Classical metalation reactions such as the metal-halogen exchange are powerful tools to construct chemical bonds between two molecules. An analogous metal-carbon exchange strategy would provide a new entry into the direct structural remodeling of core carbon frameworks, yet its development has remained highly challenging. Here we introduce a skelet...

A metal-free deaminative coupling of non-prefunctionalised benzylamines and arylboronic acids is reported. In this operationally simple reaction, a primary amine in benzylamine is converted into a good leaving group in situ using inexpensive and commercially available isoamyl nitrite as a nitrosating reagent. Lewis-acidic arylboronic acids are show...

A strategy for the palladium-catalyzed intermolecular synthesis of polysubstituted cyclopentenones is reported. The three-component reaction utilizes vinyl iodides and internal alkynes to form the carbon framework of the cyclopentenone with Cr(CO)6 serving as an easy to handle, solid CO surrogate, and a hydrosilane as a hydride source. We demonstra...

A rhodium‐catalyzed anti‐Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either (E)‐ or (Z)‐configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employing ea...

Shuttle hetero‐difunctionalization reaction, in which two chemically distinct functional groups are transferred between two molecules, has long been an unmet goal due to the daunting challenges in controlling the chemo‐, regio‐, and stereoselectivity. Herein, we disclose an electrochemistry enabled shuttle reaction (e‐shuttle) to selectively transf...

Oxygenated molecules are omnipresent in natural as well as artificial settings making the chemical modification of C–O bonds a central tool for their processing. The catalytic hydrogenolysis and oxidation of C–O bonds are particularly important reactions in this context. However, the required (super)stoichiometric terminal redox equivalents which t...

Die e‐Shuttle‐Katalyse ist ein vielversprechendes Werkzeug, um funktionelle Gruppen zwischen Molekülen hin und her zu übertragen, und zwar über einen aufeinanderfolgenden Mechanismus der gepaarten Elektrolyse. Ein seltenes Beispiel für eine Shuttle‐Heterodifunktionalisierung zur Übertragung zweier unterschiedlicher funktioneller Gruppen zwischen β‐...

e‐Shuttle catalysis is a promising tool to transfer functional groups between molecules forth and back via a consecutive paired electrolysis mechanism. A rare example of shuttle hetero‐difunctionalization to transfer two distinct functional groups between β‐halosulfides and unsaturated hydrocarbons is shown by Siegfried R. Waldvogel, Bill Morandi e...

We report a convenient protocol for a nitrogen atom insertion into indenes to afford isoquinolines. The reaction uses a combination of commercially available (diacetoxy¬iodo)benzene (PIDA) and ammonium carbamate to furnish a wide range of isoquinolines. Various substitution patterns and commonly used functional groups are well tolerated and the ope...

Many methods report the scission of the NO bonds of aromatic heterocycles and their subsequent functionalization. Oxidative addition is one of the presumed pathways through which aromatic NO bond activation with transition metals is achieved. We report the first well-defined pathway of (benz)isoxazole's aromatic NO bond activation through oxidative...

Shuttle hetero‐difunctionalization reaction, in which two chemically distinct functional groups are transferred between two molecules, has long been an unmet goal due to the daunting challenges in controlling the chemo‐, regio‐, and stereoselectivity. Herein, we disclose an electrochemistry enabled shuttle reaction ( e ‐shuttle) to selectively tran...

A rhodium‐catalyzed anti‐Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either ( E )‐ or ( Z )‐configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employin...

A rhodium-catalyzed anti-Markovnikov hydroiodination of aromatic and aliphatic terminal alkynes is reported. Depending on the choice of ligand and substrate, either (E)- or (Z)-configured alkenyl iodides are obtained in high to exclusive isomeric purity. The reaction exhibits a broad substrate scope and high functional group tolerance, employing ea...

Alkylpalladium complexes are important intermediates in several industrially relevant catalytic reactions, such as the Mizoroki–Heck reaction, alkyl C–H activation and ethylene polymerization. β-elimination—of either a hydride (β-Η) or a heteroatom (β-Χ)—is the most common decomposition pathway for these intermediates; this can either lead to the d...

Compared with peripheral late-stage transformations mainly focusing on carbon–hydrogen functionalizations, reliable strategies to directly edit the core skeleton of pharmaceutical lead compounds still remain scarce despite the recent flurry of activity in this area. Herein, we report the skeletal editing of indoles through nitrogen atom insertion,...

Electrophilic aminating reagents have seen a renaissance in recent years as effective nitrogen sources for the synthesis of unprotected amino functionalities. Based on their reactivity, several noble and non-noble transition metal catalysed amination reactions have been developed. These include the aziridination and difunctionalisation of alkenes,...

Functional group metathesis is an emerging field in organic chemistry with promising synthetic applications. However, no complete mechanistic studies of these reactions have been reported to date, particularly regarding the nature of the key functional group transfer mechanism. Unraveling the mechanism of these transformations would not only allow...

We report a diversification strategy that enables the direct substituent exchange of tertiary phosphines. Alkylated phosphonium salts, prepared by standard alkylation of phosphines, are selectively dearylated in a nickel-catalysed process to access alkylphosphine products via a formal substitution at the phosphorus center. The reaction can be used...

Advances in the field of late-stage functionalization have expedited lead-structure discovery and established new opportunities to access valuable molecules. Although many peripheral late-stage transformations, mainly focusing on C–H functionalizations, have been reported, reliable strategies to directly edit the core skeleton of lead compounds hav...

Carbon dioxide (CO2) impacts every aspect of life, and numerous sensing technologies have been established to detect and monitor this ubiquitous molecule. However, its selective sensing at the molecular level remains an unmet challenge, despite the tremendous potential of such an approach for understanding this molecule's role in complex environmen...

The reversible formation of carbon–carbon bonds is key in many catalytic reactions but its mechanism is challenging to study. Now, a detailed investigation into a palladium-catalysed diastereoconvergent reaction uncovers a unique mechanism in which reversible β-carbon elimination is crucial for productive catalysis.

Numerous important transition metal-catalysed reactions rely on stoichiometric quantities of an exogenous base to enable catalytic turnover. Despite playing a fundamental role, the base poses major challenges, such as restricting the accessible chemical space or causing heterogeneous reaction mixtures. Here we introduce a unifying strategy that eli...

We report a general diversification strategy for phosphines that enables the rapid discovery of new ligands. Alkylated phosphonium salts, prepared by standard alkylation of phosphines, are selectively dearylated in a nickel-catalyzed process to access alkylated phosphine products via a formal substitution at the phosphorus center. The reaction can...

10 Alkylpalladium complexes are important intermediates in several industrially relevant catalytic reactions such as the Mizoroki-Heck, alkyl C-H activation and ethylene polymerisation. Beta-elimination-of either a hydride (β-Η) or a heteroatom (β-Χ)-is the most common decomposition pathway for these intermediates; this can either promote the desir...

Herein, we study the mechanism of iron-catalyzed direct synthesis of unprotected aminoethers from olefins by a hydroxyl amine derived reagent using a wide range of analytical and spectroscopic techniques (Mössbauer, Electron Paramagnetic Resonance, Ultra-Violet Visible Spectroscopy, X-ray Absorption, Nuclear Resonance Vibrational Spectroscopy, and...

Porous organic materials (polymers and COFs) have shown a number of promising properties; however, the lability of their linkages often limits their robustness and can hamper downstream industrial application. Inspired by the outstanding chemical, mechanical, and thermal resistance of the 1D polymer poly(phenylene sulfide) (PPS), we have designed a...

In the last twenty years, nickel has successfully imprinted its role in the field of homogeneous catalysis as a valid and complementary alternative to palladium and platinum catalysts. However, compared to those, there are often many different available pathways in nickel catalysis due to the facile access of intermediate oxidation states. Among th...

Here we report a palladium‐catalysed difunctionalisation of unsaturated C−C bonds with acid chlorides. Formally, the C−COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or a tethered alkyne to generate new acid chlorides. The transformation does not require exogenous carbon monoxide, oper...

A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C–S bond...

Here we report a palladium‐catalysed difunctionalisation of unsaturated C–C bonds with acid chlorides. Formally, the C–COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or tethered alkynes to generate new acid chlorides. The transformation does not require exogenous carbon monoxide, opera...

Here we report a palladium-catalysed intermolecular difunctionalisation of unsaturated C–C bonds with acid chlorides. Specifically, the C–COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or tethered alkynes to generate new acid chlorides. The transformation does not require exogenous car...

Here we report a palladium-catalysed intermolecular difunctionalisation of unsaturated C–C bonds with acid chlorides. Specifically, the C–COCl bond of an acid chloride is cleaved and added, with complete atom economy, across either strained alkenes or tethered alkynes to generate new acid chlorides. The transformation does not require exogenous car...

The past 20 years have seen an extensive implementation of nickel in homogeneous catalysis through the development of unique reactivity not easily achievable by using noble transition metals. Many catalytic cycles propose Ni(I) complexes as potential reactive intermediates, yet the scarcity of nickel(I) precursors and the lack of a general, non-lig...

A nickel‐catalyzed thiolation of aryl nitriles has been developed to access functionalized aryl thioethers. The ligand dcype (1,2‐bis(dicyclohexylphosphino)ethane) as well as the base KOtBu (potassium tert‐butoxide) are essential to achieve this transformation. This scalable and practical process involves both a C−C bond activation and a C−S bond f...

We report an efficient and broadly applicable palladium‐catalyzed iodination of inexpensive and abundant aryl and vinyl carboxylic acids via in situ activation to the acid chloride and formation of a phosphonium salt. The use of 1‐iodobutane as iodide source in combination with a base and a deoxychlorinating reagent gives access to a wide range of...

Porous organic polymers have shown a number of promising properties; however, their application is usually hampered due to the lability of their linkages. Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulphide (PPS), we have designed a new family of 2D and 3D poly-arylthioethers, synthesised...

Porous organic polymers have shown a number of promising properties; however, their application is usually hampered due to the lability of their linkages. Inspired by the outstanding chemical, mechanical and thermal resistance of the 1D polymer polyphenylene sulphide (PPS), we have designed a new family of 2D and 3D poly-arylthioethers, synthesised...

Eine effiziente und breit anwendbare Palladium-katalysierte Iodierung günstiger und leicht verfügbarer Aryl- und Vinylcarbonsäuren durch In-situ-Aktivierung zum Säurechlorid und Bildung eines Phosphoniumsalzes wurde entwickelt. Die Verwendung von 1-Iodbutan als Iodidquelle in Kombination mit einer Base und einem Desoxychlorierungsreagenz eröffnet d...

A cascade Suzuki-Miyaura cross-coupling giving rise to 9,10-dihydrophenanthrenes has been developed. Using biaryls with unsymmetrical substitution-pattern full site-selectivity was observed. Furthermore, this cross-coupling of an alkyl 1,2-bisboronic pinacol ester proceeds...

div>A nickel-catalyzed thiolation of aryl nitriles has been developed to access functionalized aryl thioethers. The ligand dcype (1,2 Bis(dicyclohexylphosphino)ethane) as well as the base KOtBu (potassium tert-butoxide) are essential to achieve this transformation. This scalable and practical process involves both a C–C bond activation and a C–S bo...

p> Transition metal catalysis has revolutionized our ability to precisely manipulate matter and has placed itself at the forefront of the combat against societal challenges through key discoveries in drug design, agriculture, material synthesis and environmental sciences. Numerous important transition metal catalyzed reactions rely on stoichiometri...

We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatiz...

The advent of transfer hydrogenation and borrowing hydrogen reactions paved the way to manipulate simple alcohols in previously unthinkable manners and circumvented the need for hydrogen gas. Analogously, transfer hydrocarbylation could greatly increase the versatility of tertiary alcohols. However, this reaction remains unexplored because of the c...

The direct dehydrogenation of alkanes is among the most efficient ways to access valuable alkene products. Although several catalysts have been designed to promote this transformation, they have unfortunately found limited applications in fine chemical synthesis. Here, we report a conceptually novel strategy for the catalytic, intermolecular dehydr...

We report both an intermolecular C-H amination of arenes to access N-methylanilines and an intramolecular variant for the synthesis of tetrahydroquinolines. A newly developed, highly electrophilic aminating reagent was key for the direct synthesis of unprotected N-methylanilines from simple arenes. The reactions display a broad functional group tol...

Hydroformylation, a reaction that installs both a C–H bond and an aldehyde group across an unsaturated substrate, is one of the most important catalytic reactions in both industry and academia. Given the synthetic importance of creating new C–C bonds, the development of carboformylation reactions, wherein a new C–C bond is formed instead of a C–H b...

An approach to the catalytic dehydrogenation of alkanes and heterocycles uses Ru and redox‐active ligands. A wide range of functionalized substrates afforded dehydrogenated products in good yields. Preliminary mechanistic studies suggest that a redox‐active ligand‐assisted intermolecular hydrogen atom transfer is crucial to this process. Abstract...

We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic manifold nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide and thiol-free reaction showed high functional-group tolerance and great efficiency for late-stage derivatizat...

We describe a general strategy for the intermolecular synthesis of polysubstituted cyclopentenones using palladium catalysis. Overall, this reaction is achieved via a molecular shuffling process involving an alkyne, an α,β-unsaturated acid chloride, which serves as both the alkene and carbon monoxide source, and a hydrosilane to create three new C-...

Unprotected, primary 2-azidoamines are versatile precursors to vicinal diamines, which are among the most common motifs in biologically active compounds. Herein, we report their operationally simple synthesis through an iron-catalyzed difunctionalization of alkenes. A wide array of alkene substrates are tolerated, including complex drug-like molecu...

An iron catalyzed reaction for the selective transformation of thiols (‐SH) to sulfinamides (‐SONH2) by a direct transfer of ‐O and free ‐NH2 groups has been developed. The reaction operates under mild conditions using a bench stable hydroxylamine derived reagent, exhibits broad functional group tolerance, is scalable and proceeds without the use o...

The advent of transfer hydrogenation and borrowing hydrogen reactions paved the way to manipulate simple alcohols in previously unthinkable manners and circumvent the need for hydrogen gas. Analogously, transfer hydrocarbylation could greatly increase the versatility of tertiary alcohols. However, this reaction remains unexplored because of the cha...

Allgemein verfügbare Thiole werden chemoselektiv unter Verwendung eines kostengünstigen Eisenkatalysators durch die Bildung von zwei verschiedenen neuen Bindungen (S=O und S−N) in einem einzigen Schritt zu wertvollen ungeschützten Sulfinamiden umgewandelt. Ein von Hydroxylamin abgeleitetes Reagenz fungiert als duales Oxidationsmittel und Aminogrupp...

Secondary and tertiary alkylamines are privileged substance classes that are often found in pharmaceuticals and other biologically active small molecules. Herein, we report their direct synthesis from alkenes through an aminative difunctionalization reaction enabled by iron catalysis. A family of ten novel hydroxylamine‐derived aminating reagents w...

An efficient palladium‐catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high‐value products from readily available...

The direct synthesis of unprotected secondary and tertiary alkylamines from alkenes is reported. Aminative difunctionalization was mediated by an iron catalyst to yield a family of ten hydroxylamine‐derived aminating reagents. Several medicinally relevant amine groups, such as methylamine, morpholine and piperazine, were installed through the amino...

p>Hydroformylation, a reaction which installs both a C–H bond and an aldehyde group across an unsaturated substrate, is one of the most important catalytic reactions both in industry and academia. Given the synthetic importance of creating new C–C bonds, and the widespread academic and industrial impact of hydroformylation , the development of carb...

An efficient palladium‐catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high‐value products from readily available...

p>Secondary and tertiary alkylamines are privileged substance classes which are often found in pharmaceuticals and other biologically active small molecules. Herein, we report their direct synthesis from alkenes through an aminative difunctionalization reaction enabled by iron catalysis. A family of nine novel hydroxylamine-derived aminating reagen...

Reversible catalytic reactions operate under thermodynamic control and thus establishing a selective catalytic system poses a considerable challenge. Herein, we report a reversible transfer hydrocyanation protocol that exhibits high selectivity for the thermodynamically less favorable branched isomer. Selectivity is achieved by exploiting the lower...

Herein, we report a nickel-dcype complex for the catalytic Buchwald-Hartwig amination of aryl thioethers. The protocol shows broad applicability with a variety of different functional groups tolerated under the catalytic conditions. Extensive organometallic and kinetic studies support a nickel(0)-nickel(II) pathway for this transformation and revea...