The development of divergent methods to expedite structure–activity relationship studies is crucial streamline discovery processes. We developed a rare example regiodivergent ring expansion access two regioisomers from common starting material. To enable this regiodivergence, we identified distinct reaction conditions for transforming oxindoles into quinolinone isomers. presented proved be compatible with variety functional groups, which enabled the late-stage diversification bioactive as...

Primary amines are essential constituents of biologically active molecules and versatile intermediates in the synthesis drugs agrochemicals. However, their preparation from easily accessible alkenes remains challenging. Here, we report a general strategy to access primary through an operationally simple iron-catalyzed aminochlorination reaction. A stable hydroxylamine derivative benign sodium chloride act as respective nitrogen chlorine sources. The reaction proceeds at room temperature...

Abstract A nickel‐catalyzed aryl thioether metathesis has been developed to access high‐value thioethers. 1,2‐Bis(dicyclohexylphosphino)ethane (dcype) is essential promote this highly functional‐group‐tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield an unusual example of ring‐closing that does not involve alkene bonds. In‐depth organometallic studies support a reversible Ni 0 /Ni II pathway product formation. Overall, work only provides...

We describe a new functional group metathesis between aryl nitriles and thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good excellent yields. Furthermore, the cyanide- thiol-free reaction shows high tolerance great efficiency for late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility utility multistep synthesis.

Abstract Secondary and tertiary alkylamines are privileged substance classes that often found in pharmaceuticals 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 were designed for the installation several medicinally relevant amine groups, such as methylamine, morpholine piperazine, aminochlorination...

Herein, we report a nickel–1,2-bis(dicyclohexylphosphino)ethane (dcype) complex for the catalytic Buchwald–Hartwig amination of aryl thioethers. The protocol shows broad applicability with variety different functional groups tolerated under conditions. Extensive organometallic and kinetic studies support nickel(0)–nickel(II) pathway this transformation revealed oxidative addition as resting state cycle. All isolated intermediates have proven to be catalytically kinetically competent...

Many elegant asymmetric syntheses of enantioenriched tertiary alcohols have been developed, and both the transition metal-catalyzed radical-based peripheral functionalization attracted intensive research interest in recent years. However, directly editing tetrasubstituted carbons remains challenging. Herein, we report a Pd-catalyzed migratory fluoroarylation reaction that converts to α-fluorinated alkyl ethers good excellent yields. An unprecedented 1,2-aryl/PdIV dyotropic rearrangement...

A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized 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 C–S bond activation and C–C formation. scalability, low catalyst reagents loadings, high functional group tolerance have enabled late-stage derivatization polymer...

The intramolecular carbothiolation of unsaturated hydrocarbons using a palladium–NHC catalyst (NHC = N-heterocyclic carbene) is described. Herein, single system enables both initial activation C(sp2)–S bond through oxidative addition and formation C(sp3)–S terminal reductive elimination, unlocking completely atom-economical transfer across alkenes. reaction tolerates variety different functional groups, exhibits excellent chemoselectivity in the presence competing thioether moieties, can be...

Abstract A nickel‐catalyzed thiolation of aryl nitriles has been developed to access functionalized thioethers. The ligand dcype (1,2‐bis(dicyclohexylphosphino)ethane) as well the base KO t Bu (potassium tert ‐butoxide) are essential achieve this transformation. This scalable and practical process involves both a C−C bond activation C−S formation. Furthermore, reaction shows high functional‐group tolerance enables late‐stage functionalization important molecules.

Abstract Secondary and tertiary alkylamines are privileged substance classes that often found in pharmaceuticals 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 were designed for the installation several medicinally relevant amine groups, such as methylamine, morpholine piperazine, aminochlorination...

Abstract Für die Synthese von hochwertigen Thioethern wurde eine Nickel‐katalysierte Arylthioether‐Metathese entwickelt. 1,2‐Bis(dicyclohexylphosphino)ethan (dcype) ist essentiell, um diese Reaktion mit breiter Kompatibilität funktioneller Gruppen zu ermöglichen. Weiterhin konnten synthetisch anspruchsvolle Makrocyclen in guter Ausbeute einem seltenen Beispiel für Ringschlussmetathese ohne Doppelbindungen erhalten werden. Umfassende metallorganische Untersuchungen belegen einen reversiblen...

We describe a new functional group metathesis between aryl nitriles and thioethers. The catalytic manifold nickel/dcype is essential to achieve this fully reversible transformation in good excellent yields. Furthermore, the cyanide thiol-free reaction showed high functional-group tolerance great efficiency for late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrated its versatility utility multistep synthesis.

A nickel-catalyzed thiolation of aryl nitriles has been developed to access functionalized thioethers. The ligand dcype (1,2 Bis(dicyclohexylphosphino)ethane) as well the base KOtBu (potassium tert-butoxide) are essential achieve this transformation. This scalable and practical process involves both a C–C bond activation C–S formation. Furthermore, reaction shows high functional-group tolerance enables late-stage functionalization important molecules.

<div>A nickel-catalyzed thiolation of aryl nitriles has been developed to access functionalized thioethers. The ligand dcype (1,2 Bis(dicyclohexylphosphino)ethane) as well the base KOtBu (potassium tert-butoxide) are essential achieve this transformation. This scalable and practical process involves both a C–C bond activation C–S formation. Furthermore, reaction shows high functional-group tolerance enables late-stage functionalization important molecules.</div>

A nickel-catalyzed carbon-sulfur bond metathesis has been developed to access high-value thioethers. 1,2-bis(dicyclohexylphosphino)ethane (dcype) is essential promote this highly functional group tolerant reaction. Further, synthetically challenging macrocycles could be obtained in good yield an unusual example of ring-closing which does not involve alkene bonds. In-depth organometallic studies support a reversible Ni(0)-Ni(II) pathway product formation. Overall, work only disclose more...

A nickel-catalyzed carbon-sulfur bond metathesis has been developed to access high-value thioethers. 1,2-bis(dicyclohexylphosphino)ethane (dcype) is essential promote this highly functional group tolerant reaction. Further, synthetically challenging macrocycles could be obtained in good yield an unusual example of ring-closing which does not involve alkene bonds. In-depth organometallic studies support a reversible Ni(0)-Ni(II) pathway product formation. Overall, work only disclose more...

Secondary and tertiary alkylamines are privileged substance classes which often found in pharmaceuticals 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 reagents was designed for the installation several medicinally relevant amine groups, such as methylamine, morpholine piperazine, aminochlorination alkenes. The...

We describe a new functional group metathesis between aryl nitriles and thioethers. The catalytic manifold nickel/dcype is essential to achieve this fully reversible transformation in good excellent yields. Furthermore, the cyanide thiol-free reaction showed high functional-group tolerance great efficiency for late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrated its versatility utility multistep synthesis.

<p>Secondary and tertiary alkylamines are privileged substance classes which often found in pharmaceuticals 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 reagents was designed for the installation several medicinally relevant amine groups, such as methylamine, morpholine piperazine, aminochlorination...