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Herein, for the first time, we disclose the gold‐catalyzed alkoxy‐carbonylation of aryl and vinyl iodides utilizing ligand‐enabled Au(I)/Au(III) redox catalysis. The present methodology is found to be general, efficient, employs mild reaction conditions and showcases a broad substrate scope even with structurally complex molecules. Density functional theory (DFT) calculations revealed mechanistic pathways distinct from those of conventional transition metal‐catalyzed carbonylation reactions. [ABSTRACT FROM AUTHOR]

A chemo- and regioselective hydroarylation of vinylsilanes with (hetero)aryl iodides under Ni–H catalysis is reported. This mild and straightforward protocol furnishes the anti-Markovnikov products in good yields as single regioisomers. This study demonstrates excellent control over the chemoselectivity and complements existing methods for the construction of homobenzylic silanes. [ABSTRACT FROM AUTHOR]

The synthesis of unsymmetrical diorganyl selanes was accomplished under electrochemical conditions in an undivided cell utilizing a magnesium cathode and a carbon anode made out of aryl and alkyl iodides and diselanes. This electrochemical cross-electrophile coupling (eXEC) was accomplished using a simple nickel catalyst formed in situ out of Ni(acac)2 and 2,2′-bipyridine in DMF at ambient temperatures. The reaction showed good functional group compatibility, and heteroaryl iodides, such as thiophene or pyridine derivatives, were well accepted. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Key Scientists Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s) that often change the physicochemical and biological properties of organic molecules. Transition‐metal‐mediated cross‐electrophile coupling between carbon electrophiles and fluoroalkyl electrophiles has emerged as a straightforward and efficient route for the synthesis of a wide range of fluoroalkylated compounds because of its synthetic convenience without the tedious synthesis of organometallic reagents. Moreover, alkenes or alkynes‐involved three‐component cross‐electrophile couplings provide rapid and effective access to carbonfunctionalized fluoroalkylated alkanes and alkenes. Herein, we comprehensively summarize the transition‐metal‐mediated reductive fluoroalkylation of diverse carbon electrophiles through a historical perspective, including trifluoromethylation, difluoroalkylation, monofluoroalkylation, and so on. Different transition metals (Cu, Ni, etc.) and strategies are discussed, in which nickel‐catalyzed reductive fluoroalkylation reactions represent an attractive and efficient synthetic route to site‐selectively access organofluorine compounds.As early as 1965, McLoughlin and Thrower finished the first stoichiometric copper‐mediated fluoroalkylation of aromatic iodides with fluoroalkyl iodides. However, excess aromatic iodides and elevated temperature were used for this method. In 1969, Kobayashi and Kumadaki reported studies on the copper‐mediated trifluoromethylation of aromatic halides with excess trifluoromethyl iodide. After more than four decades, the Zhang group developed a nickel‐catalyzed β‐fluorinated alkylation of (hetero)aryl iodides with fluoroalkylated secondary alkyl bromides in 2015, and a nickel‐catalyzed difluoromethylation of (hetero)aryl chlorides with chlorodifluoromethane ClCF2H in 2017. The Zhang group also developed enantioselective nickel‐catalyzed reductive alkyl‐arylation of 3,3,3‐trifluoropropene with (hetero)aryl and tertiary alkyl iodides. In 2018, the MacMillan group developed a novel copper/photoredox dual catalytic system for the trifluoromethylation of aryl bromides or alkyl bromides with (S)‐(trifluoromethyl) dimesitylsulfonium triflate in the presence of tris‐(trimethylsilyl) silanol. They also developed a nickel/photoredox catalyzed difluoromethylation of aryl bromides in the presence of silane. During this time, the Wang group reported a nickel‐catalyzed monofluoroalkylation of aryl halides with monofluoroalkyl halides. From 2021 to 2023, the same group further developed a series of enantioselective nickel‐catalyzed trifluoroalkylation of aryl, alkenyl, and acyl halides. Moreover, nonfluorinated alkenes or alkynes could also be used in three‐component cross‐electrophile couplings. In 2018, the Chu group reported a nickel‐catalyzed fluoroalkyl‐acylation of alkenes with acyl chlorides and fluoroalkyl iodides. Later, they developed a nickel‐catalyzed enantioselective fluoroalkyl‐arylation of unactivated alkenes tethering with a pendant chelating group. In 2019, the Chaładaj group reported a palladium‐catalyzed reductive perfluoroalkyl‐arylation of alkynes with perfluoroalkyl and aryl iodides. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A visible light photocatalytic [3+2] cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein. By merging halogen atom transfer (XAT) and hydrogen atom transfer (HAT), alkyl/aryl iodides serve as a formal diradical precursor and add across C‐C triple bonds to deliver a number of functionalized cyclopentanes in moderate to high yields with exceptional regio‐ and diastereoselectivity. A reductive radical‐polar crossover mechanism, involving the cascade XAT, radical addition, 1,5‐HAT, polar effect‐promoted 5‐endo annulation, single electron transfer (SET) reduction, and protonation, may account for this unprecedented dehalogenative [3+2] cycloaddition. This work not only expands the repertoire of the traditional RATC methodology, but also provides a robust platform for the expedient assembly of cyclopentanes, a valuable structural motif in the realms of medicinal chemistry and material sciences. [ABSTRACT FROM AUTHOR]

In this research, we first fabricated Fe3O4@Dop-Triazine-CuCl2 nanocatalyst by simple method, then its catalytic activity was investigated in the preparation of various derivatives of aryl-heteroaryl and di-heteroaryl selenides through C–Se coupling reactions of aryl iodides with powder selenium and various derivatives of heterocyclic compounds (with active C–H bonds). The catalyst exhibited spherical morphology with a diameter of approximately 20–30 nm and a magnetic saturation moment of 50.032 emu/g. The hydrocarbon content was measured to be around 12% by weight. In this method, a wide range of aryl-heteroaryl and di-heteroaryl selenides (36 examples) were synthesized with high yields (85–97%) using catalytic amount of the Fe3O4@Dop-Triazine-CuCl2 nanomaterial in the presence of KHCO3 in [BMIM]PF6 as solvent. This method has several remarkable features, which can be mentioned as follows: the synthesis of aryl-heteroaryl and di-heteroaryl selenide derivatives with high yields, performing the reactions in a suitable time (4 h), the applicability of this catalytic system for a wide range of substrates, the use of ionic liquid as solvent, high efficiency of Fe3O4@Dop-Triazine-CuCl2 catalyst, simple separation and high reusability of nanocatalyst. [ABSTRACT FROM AUTHOR]

Directed Pd‐catalysed β‐(hetero)arylation of the 7‐oxabicyclo[2.2.1]heptane framework is described. Arylated products were formed in up to 99 % yield, and heteroarylated products in up to 88 % yield with complete diastereoselectivity. Different minor diarylated side products were formed, depending on whether electron deficient aryl or pyridyl iodides were used as the coupling partners. Cleavage of the 8‐aminoquinoline directing group provided small bridged compounds that may be of value in fragment based drug discovery. [ABSTRACT FROM AUTHOR]

Enantioselective transformations of hydrocarbons to three-dimensional chiral molecules remain a significant challenge in synthetic chemistry. This study uses asymmetric paired oxidative and reductive catalysis to promote the enantioselective alkylarylation of olefins through the functionalization of C(sp3)−H bonds in alkanes. This asymmetric photoelectrocatalytic approach enables the facile construction of a wide range of enantioenriched α-aryl carbonyls with excellent enantioselectivity (up to 96% ee) from readily accessible starting materials. Notably, aryl bromides, aryl iodides, and even aryl chlorides were compatible with the developed catalytic system. Mechanistic studies reveal that alkanes and electrophiles are simultaneously activated on the electrodes. The pursuit of methods to rapidly construct of molecular complexity from easy-to-obtain starting materials drives chemical synthesis. Here, the authors report an asymmetric three-component coupling of simple alkanes, alkenes, and aryl halides, using asymmetric paired oxidative and reductive catalysis. [ABSTRACT FROM AUTHOR]

Given her unrivalled proficiency in the synthesis of all molecules of life, nature has been an endless source of inspiration for developing new strategies in organic chemistry and catalysis. However, one feature that remains thus far beyond chemists' grasp is her unique ability to adapt the productivity of metabolic processes in response to triggers that indicate the temporary need for specific metabolites. To demonstrate the remarkable potential of such stimuli‐responsive systems, we present a metabolism‐inspired network of multicatalytic processes capable of selectively synthesising a range of products from simple starting materials. Specifically, the network is built of four classes of distinct catalytic reactions—cross‐couplings, substitutions, additions, and reductions, involving three organic starting materials—terminal alkyne, aryl iodide, and hydrosilane. All starting materials are either introduced sequentially or added to the system at the same time, with no continuous influx of reagents or efflux of products. All processes in the system are catalysed by a multifunctional heteronuclear PdII/PtII complex, whose performance can be controlled by specific additives and external stimuli. The reaction network exhibits a substantial degree of orthogonality between different pathways, enabling the controllable synthesis of ten distinct products with high efficiency and selectivity through simultaneous triggering and suppression mechanisms. [ABSTRACT FROM AUTHOR]

The application of a series of hydroxyl‐containing Schiff‐base ligands in the synthesis of zinc complexes is reported. The substituents on the benzene rings, the positions of the C=N double bonds, and the ratio of the ligands to ZnEt2 affect the nuclearities of the zinc compounds. Complexes of various nuclearities were prepared, ranging from trinuclear cluster and dinuclear complexes to mononuclear compounds. Treatment of HL1 (HL1=2‐(((1‐(2‐(dimethylamino)ethyl)‐1H‐pyrrol‐2‐yl)methylene) amino)phenol) with one equivalent of ZnEt2 generated a trinuclear compound [(L1)ZnEt]3 ⋅ 0.8Tol (1 ⋅ 0.8Tol). Three dinuclear compounds [(L2)ZnEt]2 ⋅ Tol (2 ⋅ Tol), [(L3)ZnEt]2 (3), and [(L4)ZnEt]2 (4), and two mononuclear complexes [(L5)ZnEt] (5) and [(L6)ZnEt] (6) were formed by the reactions of HL2−HL6, respectively, with ZnEt2. The HL2−HL6 ligands were obtained by slightly modifying the backbone of the HL1 ligand. Three homoleptic compounds [(L1)2Zn] ⋅ THF (7 ⋅ THF), [(L4)2Zn] ⋅ Tol (8 ⋅ Tol), and [(L5)2Zn] (9) were afforded by changing the ratio of the ligands to ZnEt2 from 1 : 1 (compounds 1 ⋅ 0.8Tol, 4 and 5) to 1 : 0.5. The catalytic potential of all nine compounds for the borylation of aryl iodides by B2Pin2 was explored. The catalytic activity of 2 ⋅ Tol was the highest. The reactions catalyzed by 2 ⋅ Tol possess the features of high functional group tolerance and broad substrate scope. [ABSTRACT FROM AUTHOR]

Efficient charge generation is essential for tandem organic light-emitting diode (OLED) devices. In this study, we introduce a p-type copper iodide (CuI) layer within the charge generation layer (CGL) that exhibits high charge generation efficiency in tandem OLED devices. Briefly, CuI is deposited as a thin layer via thermal evaporation technique. X-ray diffraction (XRD) analysis reveals the formation of γ-CuI, and the ultraviolet-visible (UV-Vis) spectral analysis demonstrates outstanding optical transparency (∼95%) of the deposited CuI films in the visible range. The current-voltage (I-V) and capacitance-voltage (C-V) analyses show that the p-type CuI layer is a vital and excellent charge generator and enhances the current density significantly. The tandem OLED device fabricated using Bphen:Liq/CuI/HAT-CN as the CGL results in a substantial 1.9-fold increase in current efficiency compared to the single-unit OLED device, approaching the theoretical two-fold increase. These findings highlight the potential of CuI as a promising p-type material for CGL design in tandem OLED devices. [ABSTRACT FROM AUTHOR]

During the last decade, research on the preparation of nano-catalysts, especially magnetic nano-catalysts, and their application in chemical reactions has become an attractive topic in organic synthesis. Nitriles are valuable compounds that are important in industrial, biological, and pharmaceutical processes. On the other hand, tetrazoles are heterocyclic compounds that have valuable pharmacological and biological properties. Therefore, developing new, environmentally friendly, and efficient catalytic systems for synthesizing nitriles and tetrazoles is needed. In this research work, we successfully fabricated Pd (0) complex immobilized on Fe3O4 nanoparticles modified with 3-amino-2-(aminomethyl)propanoic acid and imidazole [Fe3O4@SiO2-AAPA/Imid-Pd(0)] and investigated its catalytic activity in the preparation of aryl nitriles and 5-substituted-1H-tetrazoles from aryl iodides. In this attractive methodology, we first prepared different aryl nitrile derivatives from the cyanation of aryl halides and then prepared a broad range of 5-substituted-1H-tetrazoles through the condensation of the as-prepared aryl nitriles with sodium azide. The experimental results revealed that this catalyst could be reused for more than 8 consecutive runs without losing activity. Among the outstanding features of this method for the synthesis of aryl nitriles and tetrazoles, the following can be mentioned: the synthesis of products with high yields in suitable times, performing the reactions in an environmentally friendly solvent, the applicability of the method for a wide range from the substrates, easy separation of the Fe3O4@SiO2-AAPA/Imid-Pd(0) catalyst from the reaction mixture and high reusability of the catalyst. [ABSTRACT FROM AUTHOR]

This work reports the synthesis and characterization of Nanosized-Ni doped montmorillonite heterocatalyst and its application for Suzuki Miyaura cross coupling of aryl iodides with aryl boronic acids. The catalyst is highly selective and did not give any other byproducts. The reaction was complete within 24 h with > 98% yield. Nickel was uniformly dispersed on the catalyst with approximately 4.0 ± 2 nm clusters of Ni. The solvent, base, catalyst loading, and catalyst precursors were varied to obtain optimum reaction conditions for highest yield. The catalyst was recovered and reused for reactions demonstrating excellent recyclability with high yield. Ni doped montmorillonite catalyst is very effective for Suzuki Miyaura cross coupling reactions and can be used to replace expensive Pd-based catalysts with earth abundant and inexpensive Ni-based catalysts. [ABSTRACT FROM AUTHOR]

This study focuses on the design, eco‐friendly synthesis, and characterization of several novel three‐legged triphenylamine derivatives. By performing Sonogashira couplings of functionalized aryl iodides with tris(4‐ethynylphenyl)amine in glycerol, a readily available bio‐derived solvent, we achieved the synthesis of target products in short times and high yields, up to 94 %, with consistently lower E‐factors and reduced costs compared to standard conditions using toluene as the reaction medium. The target molecules possess a D‐(π‐A)₃ or D‐(π‐D)₃ structure, where an electron‐donating core connects to three electron‐donating (D) or electron‐accepting (A) peripheral aromatic subunits through an acetylene spacer. Their main optical and electronic properties have been determined experimentally and by DFT simulations and suggest a possible implementation in energy conversion technologies such as luminescent solar concentrators (LSCs) and perovskite solar cells (PSCs). [ABSTRACT FROM AUTHOR]

Taking iodine-peroxide and diphenyldiselelen ether as raw materials, dimethyl sulfoxide as solvent, ammonium iodide and potassium tert-butoxide as catalysts, C Se bond coupling was formed at room temperature, and 11 selenium aryl peroxides were synthesized. By using HNMR spectroscopy, CNMR spectroscopy and mass spectrometry, the products were characterized and analyzed separately. Through a series of control experiments, the reaction was determined to be ionic and the corresponding reaction mechanism was inferred. The results show that 11 selenium aryl peroxides are all yellow liquid. The yield is 68%~85%. [ABSTRACT FROM AUTHOR]

Quantitative molecular structure‐reactivity models are useful for generating predictions to guide synthesis design, and in formulating and testing mechanistic hypotheses. We report an expanded multivariate linear regression (MLR) model for the rate of (hetero)aryl (pseudo)halide oxidative addition to L2Pd(0), here exemplified by Pd(PCy3)2. This builds on a prior model from our group, with additional substrate classes (aryl chlorides and iodides) and reaction solvents (THF, toluene, THF/DMF mixture). Overall solvent effects across the entire substrate set are minimal under these conditions, enabling a unified MLR model without introduction of new molecular descriptors beyond the original five. Examining the mechanistic origin of the two molecular electrostatic potential (ESP) descriptors led to generation of a simpler, four descriptor model that is suitable for aryl halides, but not for 2‐halopyridines. Using this model we identified a mechanistic outlier, 2‐pyridyl triflate, which undergoes a nucleophilic displacement oxidative addition that does not involve the adjacent nitrogen atom. Finally, we discuss the relationship between C−X bond strength and oxidative addition rates, and compare the intrinsic bond strength index (IBSI) to bond dissociation enthalpy (BDE) as a bond strength descriptor. [ABSTRACT FROM AUTHOR]

A low‐valent tungsten catalyzed carbonylative Sonogashira coupling reactions has been established. The present protocol utilizes inexpensive and readily available W(CO)6 as precatalyst and proceeds in the presence of atmospheric CO, providing a practical method to a series of functionalized alkynones and indoxyls compounds under mild reaction conditions. Moreover, the simple reaction system, good functional group tolerance and broad substrate scope enable the application of this transformation in the synthesis of functionalized carbonyl‐containing molecules. [ABSTRACT FROM AUTHOR]

Herein, we disclose the first report on gold‐catalyzed C(sp2)‐CN cross‐coupling reaction by employing a ligand‐enabled Au(I)/Au(III) redox catalysis. This transformation utilizes acetone cyanohydrin as a nucleophilic cyanide source to convert simple aryl and alkenyl iodides into the corresponding nitriles. Combined experimental and computational studies highlighted the crucial role of cationic silver salts in activating the stable (P,N)‐AuCN complex towards the oxidative addition of aryl iodides to subsequently generate key aryl‐Au(III) cyanide complexes. [ABSTRACT FROM AUTHOR]

(Hetero)biaryls are fundamental building blocks in the pharmaceutical industry and rapid access to these scaffolds is imperative for the success of numerous medicinal chemistry campaigns. Herein, a highly general, mild, and chemoselective reductive cross‐electrophile coupling between (hetero)aryl iodides and heteroaryl bromides is reported. By employing more reactive (hetero)aryl halides, a broad range of successful substrates (45 examples) were identified. The reaction was also found to be chemoselective for C(sp2)‐C(sp2) bond formation between (hetero)aryl iodides and bromides over (hetero)aryl chlorides, which were generally inert under the described reaction conditions. The efficiency of the procedure is also further demonstrated in parallel synthesis library format, on gram scale, as well as in the formal synthesis of Ruxolitinib, a potent JAK inhibitor. As such, we anticipate this method will find widespread utility in the assembly of (hetero)biaryls for medicinal chemistry efforts. [ABSTRACT FROM AUTHOR]

Palladium‐catalyzed thioesterification of (aza)indole‐tethered aryl iodides, Mo(CO)6, and sulfonyl chlorides is reported. A series of C2 thioester‐group substituted indoline‐fused ring compounds are constructed by an intramolecular Heck cyclization and carbonylation chemistry involving N‐(2‐iodobenzoyl)indole. The salient features of this three‐component cascade sequence include the use of solid Mo(CO)6 as the carbon monoxide source and good functional group tolerance. [ABSTRACT FROM AUTHOR]

A palladium-catalyzed one-pot amino-sulfonylation of aryl iodide derivatives with thiourea dioxide, PdCl2 dppf, and one-pot added hydroxylamine- O -sulfonic acid is presented. This amino-sulfonylation gave structure diversity to aryl primary sulfonamides and features good functional group compatibility, mild reaction conditions, excellent regioselectivity, and moderate to good yields. The robustness and potential of this method have also been successfully demonstrated by late-stage elaboration and gram-scale reaction. This approach achieves the divergent construction of the complex core structures that are prevalent in highly valuable natural products such as Sulpiride, Venetoclax, and Furosemide-. [ABSTRACT FROM AUTHOR]

An efficient and broadly applicable rhodium‐catalyzed direct ortho‐arylation of anilines with aryl iodides relying on readily available aminophosphines as traceless directing groups is reported. Its scope and functional group compatibility were both found to be quite broad as a large variety of both aminophosphines and (hetero)aryl iodides, including complex ones, could be utilized. The ortho‐arylated anilines could be obtained in high average yields, without any competing diarylation and with full regioselectivity, which constitutes a major step forward compared to other processes. The reaction is moreover not limited to aryl iodides, as an aryl bromide and a triflate could be successfully used, and could be extended to diarylation. Mechanistic studies revealed the key and unique role of the aminophosphine, acting not only as a substrate but also as a ligand for the rhodium catalyst. [ABSTRACT FROM AUTHOR]

This work describes a novel iron‐catalysed approach for the synthesis of aryl‐substituted benzimidazoles and benzoxazoles. The methodology employs reductive carbonylation using readily available aryl iodides and aryl amines as precursors, with carbon monoxide serving as the efficient carbonyl source. The reaction proceeds under mild conditions with the addition of hydrosilanes and bases. Notably, aryl aldehydes are generated in situ from the aryl iodides, which subsequently react with o‐phenylenediamine or 2‐aminophenol to afford the desired products in high yields. The structures of the synthesized benzimidazoles and benzoxazoles were confirmed using 1H and 13C NMR spectroscopy and mass spectrometry. [ABSTRACT FROM AUTHOR]

This document provides detailed information on the synthesis and characterization of various compounds, including (E)-1,1-Diethoxyhexadec-11-en-9-yne, (E)-1,1-Diethoxytetradec-8-en-10-yne, (E)-1,1-Diethoxypentadec-9-en-11-yne, 9-tert-Butoxynon-1-yne, and (E)-9-tert-Butoxy-1-iodonon-1-ene. The data presented can be used by researchers studying these compounds for various applications. The document includes information on the reaction conditions, yields, and spectroscopic data for each compound, and the procedures involve specific reagents and catalysts to reduce triple bonds in the compounds. The resulting products are then purified and extracted using various techniques. [Extracted from the article]

We describe herein a method for transition‐metal‐free (hetero)arylsulfonylation of 1‐iodopyrrolo[1,2‐a]quinoxalines with sodium arylsulfinates. The corresponding aryl iodides were in situ prepared from eletrophilic iodination of C1−H bonds in pyrrolo[1,2‐a]quinoxalines with N‐iodosuccinimide. The ensuing sulfonylation only required DMSO as solvent and completed after 15 min. Many arylsulfinates bearing chloro, bromo, methylsufonyl, acetamide, and nitro groups were competent substrates. Heteroarylsulfonylation of pyrrolo[1,2‐a]quinoxalines were also feasible. [ABSTRACT FROM AUTHOR]

This article explores the synthesis of 1,2-diketones, which are important compounds in the pharmaceutical and chemical industries. Traditional methods have limitations, so researchers have been investigating new strategies. The article focuses on the use of palladium-catalyzed carbonylation reactions and the development of a recyclable heterogeneous palladium catalyst. The study provides detailed experimental procedures and optimization of reaction conditions. [Extracted from the article]

The given text discusses a recent article in the journal Synthesis that explores the synthesis of tetrasubstituted olefins, which are important in drugs and organic materials. The article proposes a method for synthesizing fully substituted olefins with multiple aryl substituents using a weakly coordinating directing group. It provides details on the experimental procedure, optimization, substrate scope, and potential applications of the method. Additionally, the text provides information on the synthesis and characterization of various chemical compounds, including their physical properties and spectroscopic data. The authors of the article are researchers from China, and their work focuses on C-H bond functionalization reactions. This information can be valuable for researchers studying organic chemistry and synthesis methods. [Extracted from the article]

The covalent organic frameworks/polymers configurated with metal‐N4 conjugated structures offer an exceptional platform for efficient electrochemical CO2 reduction reaction (eCO2RR). However, understanding the impact of the structure‐mediated local microenvironment and integrating CO2 electroreduction with follow‐up utilization toward extending chemical valorization of CO2 are still far from sufficient. Herein, a set of covalent phenanthroline‐porphyrin polymers are designed to decode the microenvironment modulation originating from built‐in structures, and the optimized one delivered an extraordinary performance for eCO2RR with ≈100% Faradaic efficiency of CO under stabilized CO2‐electrolysis of 70 h. The experimental and theoretical analyses suggest that the regulation of the Co‐N4 electronic structures and microenvironment convoys the stabilized formation of key reaction intermediate *COOH. Furthermore, through CO‐mediated electro/thermocatalytic tandem processes, the aminocarbonylation of aryl iodides and amines with high yields has been convincingly implemented over the coordinated Pd sites, which is remarkably helpful to propel extending chemical valorization of CO2. [ABSTRACT FROM AUTHOR]

We have found that amines significantly accelerate iodide substitution in CpFe(CO)2I (1) (Cp = η5-cyclopentadienyl) with phosphines and allow the synthesis of new complexes that are not available through reactions carried out without an amine. The reaction of equimolar amounts of 1 and triphenylphosphine in toluene containing DIPA afforded [CpFe(CO)2PPh3]+I− within 5 min at room temperature in 72% yield (90% after 24 h). DIPA and pyrrolidine gave the highest yields of the tested amines. We performed a similar reaction using model bisphosphines 1,3-bis(diphenylphosphino)ethane (dppe) and 1,1′-bis(diphenylphosphino)ferrocene (dppf). The products depended on the reagent ratio and bore the CpFe(CO)2 moiety coordinated to one or two phosphine phosphorus atoms. Chelates [CpFe(CO)(dppe)]+I− (4) and [Cp2Fe2(CO)4(dppe)]2+2I− (5) were formed in 72% and 98% yield, respectively. We also performed the DIPA-catalyzed reaction of 1 with triethyl phosphite and obtained the product of an Michaelis–Arbuzov-like rearrangement, CpFe(CO)2[P(O)(OCH2CH3)2] (11). All complexes were characterized with spectroscopic analysis by NMR, FT-IR, and ESI-MS, and by XRD for three complexes. To clarify the reaction mechanism, we performed theoretical calculations of the intermolecular interactions between 1 and amine molecules. We propose two possible reaction mechanisms to explain the formation of products. [ABSTRACT FROM AUTHOR]

This article presents a new method for selectively adding carbon-based units onto nonactivated alkenes using a nickel-catalyzed reaction. The researchers used a directing-group strategy to control the regio- and diastereoselectivity of the reaction, focusing specifically on the aryalkylation of alkenes. They found that a quinolinamide directing group improved the efficiency of the reaction. The study demonstrates the potential applications of this method in the synthesis of natural products, pharmaceuticals, and agrochemicals, and provides a detailed mechanism and supporting information for further exploration. [Extracted from the article]

This article discusses the development of a practical method for Fischer indolization, a commonly used synthetic approach in chemistry. The researchers used bench-stable sodium arylhydrazine sulfonates as a substitute for arylhydrazine, which is typically used in Fischer indolization. The sodium arylhydrazine sulfonates were easily obtained from substituted anilines and could be used directly in the reaction without further purification. The method was successful in synthesizing various tetrahydrocarbazoles and tryptamine-based pharmaceutical molecules. The researchers believe that this method has potential applications in the synthesis of indole-based pharmaceutical compounds. [Extracted from the article]

Regioselective C6‐arylation of thieno[3,2‐c]pyrazoles with aryl iodides as coupling partners has been developed. This strategy was performed in the presence of Pd(OAc)2 as catalyst in combination with AgOTf as an oxidant and TFA in dimethylacetamide. In all experiments, only the C6‐arylated thieno[3,2‐c]pyrazole was isolated since its C5‐regioisomer was not observed, indicating the high regioselectivity of this approach. The catalytic system used is compatible with a variety of 3‐functionalized thieno[3,2‐c]pyrazoles and iodoaryl electrophiles, providing access to 3,6‐disubstituted thieno[3,2‐c]pyrazoles in yields ranging from 49% to 94%. [ABSTRACT FROM AUTHOR]

This document provides a summary of various methods for the synthesis of tetrasubstituted axially chiral alkenes. The methods discussed include urea group-directed organocatalytic dihalogenation, Rh(III)-catalyzed C-H activation and directing group migration, cationic rhodium(I)/H8-BINAP-catalyzed chelation-controlled cycloaddition, Cu/Pd dual catalysis for arylboration, nickel-catalyzed cross-electrophile trans-aryl-benzylation, palladium-catalyzed C-H functionalization, Pd(II)-catalyzed thioether-directed alkenyl C-H olefination, Suzuki-Miyaura cross-coupling, asymmetric N-alkylation, chiral phosphoric acid catalyzed kinetic resolution, and asymmetric allylic substitution-isomerization. The methods demonstrate broad substrate scope and high enantioselectivities, but further research is needed to explore stereodivergent synthesis and applications in pharmaceutical chemistry. [Extracted from the article]

The covalent organic frameworks/polymers configurated with metal‐N4 conjugated structures offer an exceptional platform for efficient electrochemical CO2 reduction reaction (eCO2RR). However, understanding the impact of the structure‐mediated local microenvironment and integrating CO2 electroreduction with follow‐up utilization toward extending chemical valorization of CO2 are still far from sufficient. Herein, a set of covalent phenanthroline‐porphyrin polymers are designed to decode the microenvironment modulation originating from built‐in structures, and the optimized one delivered an extraordinary performance for eCO2RR with ≈100% Faradaic efficiency of CO under stabilized CO2‐electrolysis of 70 h. The experimental and theoretical analyses suggest that the regulation of the Co‐N4 electronic structures and microenvironment convoys the stabilized formation of key reaction intermediate *COOH. Furthermore, through CO‐mediated electro/thermocatalytic tandem processes, the aminocarbonylation of aryl iodides and amines with high yields has been convincingly implemented over the coordinated Pd sites, which is remarkably helpful to propel extending chemical valorization of CO2. [ABSTRACT FROM AUTHOR]

Since the discovery of the palladium/norbornene (Pd/NBE)‐catalyzed ortho amination in 2013, escaping the limitation of only yielding tertiary anilines has been a long‐standing challenge. Here, we describe that, by carefully choosing the phosphine ligand and NBE mediator, the installation of a N‐mono‐alkylamino group becomes feasible. The reaction tolerates a wide range of aryl iodide substrates and various N‐mono‐tertiary alkylamine‐derived electrophiles. Both ipso alkenylation and alkynylation can be realized. The synthetic utility of this method is exemplified by the formation of primary amino group via selective deprotection and streamlined access to N‐heterocycles. Preliminary success of installing a bulky N‐secondary alkylamino group and a mechanistic understanding of the decomposition pathways of mono N‐alkylamine electrophiles have been obtained. [ABSTRACT FROM AUTHOR]

Research on the preparation of diallyl sulfides and selenides is always an important challenge among chemists because these compounds are of high biological, pharmaceutical, industrial and chemical importance. For this purpose, in this attractive and highly efficient approach, we wish to report that copper (I) chloride immobilized on magnetic nanoparticles modified with benzothiazole–pyrimidine ligand (Fe3O4@BTH-Pyr-CuCl) is a novel and efficient magnetically recoverable catalyst for C–S and C–Se bonds formation through reaction of a category of heterocyclic compounds with aryl iodides, sulfur and selenium sources. The structure of Fe3O4@BTH-Pyr-CuCl nanocatalyst was well identified with FT-IR, SEM, TEM, EDX, elemental mapping, TGA, XRD, VSM and ICP-OES techniques. The recycling tests confirmed that the Fe3O4@BTH-Pyr-CuCl nanocatalyst was reused for 6 times without considerable reduction in its activity. This method is almost better than other methods reported in the literature for C–S and C–Se coupling of heterocycles for the following reasons, such as the use of an environmentally friendly solvent, high yields of products, the use of a catalyst that can be separated and reused and the performance of the reaction in a shorter time, presentation of well-analysis for catalyst and full NMR for products. [ABSTRACT FROM AUTHOR]

Black-phase formamidinium lead iodide (FAPbI3), with a narrow bandgap and high thermal stability, has emerged as an in-demand material for highly efficient perovskite solar cells (PSCs). In a two-step sequential deposition, the PbI2 film plays an important role in the formation of a perovskite film with desirable qualities. This paper explores using N-methyl-2-pyrrolidone (NMP), a strong Lewis base, and N,N-dimethylformamide (DMF) as a mixed precursor solvent (DMF/NMP) of PbI2 and reports on preparing PbI2 films with a porous morphology by thermal treatment. Porous PbI2 films ensure the diffusion and sufficient reaction of the formamidinium iodide solution to form a smooth perovskite film. In addition, a dynamic spin coating method is also introduced to improve the uniformity of the perovskite film. Both methods yield a pure α-phase FAPbI3 film immediately in the unannealed state, which is necessary for the perovskite film to maintain phase stability. Finally, PSCs with a power conversion efficiency of 21.20% (0.13 cm2) are fabricated and optimized. The unencapsulated PSCs retain 90% of the initial efficiency for 1000 hours in dry air and exhibit a good thermal stability when heated to 85 °C. [ABSTRACT FROM AUTHOR]

In contrast to the well‐studied 1‐vinylcyclobutanols, the reactivity of 3‐vinylazetidin‐3‐ols 1 and 3‐vinyloxetan‐3‐ols 2 under transition metal catalysis remains largely unexplored. We report herein their unique reactivity under dual palladium and acid catalysis. In the presence of a catalytic amount of Pd(OAc)2(PPh3)2, AgTFA and triflic acid, the reaction of 1 or 2 with aryl iodides affords 2,3,4‐trisubstituted dihydrofurans, which are valuable heterocycles in organic synthesis. Mechanistic studies reveal that this arylative ring‐expansion reaction proceeds via a domino process involving Heck arylation of alkene, acid‐catalyzed transposition of allylic alcohol and ring opening of the azetidine/oxetane by an internal hydroxyl group. [ABSTRACT FROM AUTHOR]

This article provides an insider's perspective on the research laboratory of Keith Fagnou at the University of Ottawa. The author, a graduate student, describes the collaborative and mentoring atmosphere in the lab, which contributed to increased productivity. The lab's focus was on ligand design projects for direct arylation reactions, and they achieved early successes in developing optimized reaction conditions and expanding reactivity to more challenging substrates. The article also emphasizes Fagnou's dedication to mentorship and his students' successful careers in academia and the pharmaceutical industry. Overall, Fagnou's research group made significant contributions to chemistry, particularly in the areas of direct arylation and oxidative biaryl coupling reactions. [Extracted from the article]

This article discusses the synthesis of benzylamines, which are important compounds in drug discovery. The authors focus on a nickel-catalyzed cross-electrophile coupling method using N-hydroxyphthalimide esters, which yields good results and is compatible with various functional groups. The method is valuable for medicinal chemistry research and can be carried out under mild conditions using commercially available precursors. The authors acknowledge the support of the Genentech Undergraduate Summer Internship Program and dedicate the article to the late Prof. Keith Fagnou. Supporting information for the article is available online. [Extracted from the article]

We have developed a novel Ni-catalyzed reductive cross-coupling reaction of aryl bromides and alkyl iodides via a photoactive electron donor–acceptor (EDA) complex. This photo-induced process enables the efficient construction of C(sp2)–C(sp3) bonds in the absence of an external photocatalyst. Electronically and structurally diverse aryl bromides, as well as secondary and primary alkyl iodides could undergo this transformation smoothly. Natural product derivatives were employed successfully, and UV-vis spectroscopy was utilized to gain mechanistic insight. [ABSTRACT FROM AUTHOR]

C–H arylation of heterocyclic compounds is a very interesting and important research field in chemistry for the formation of C–C bonds, but unfortunately, few methods have been reported for this purpose. In this attractive and highly efficient methodology, we wish to report that copper (I) chloride immobilized on magnetic nanoparticles modified with benzothiazole-pyrimidine Ligand (Fe3O4@BTH-Pyr-CuCl) is a novel and efficient magnetically recoverable catalyst for carbon–carbon bond formation through C–H arylation of a category of heterocyclic compounds by aryl iodides in the presence of KOAc in PEG under mild conditions. Under this catalytic system, A category of heterocyclic substrates including benzo[d]oxazole, benzo[d]thiazole, 1-methyl-1H-benzo[d]imidazole, 2,5-diphenyloxazole, benzofuran, 2-phenyl-1,3,4-oxadiazole and 2-phenylimidazo[1,2-a]pyridine were used as substrate and the desired products were prepared with high to excellent yields. Reusability tests revealed that the Fe3O4@BTH-Pyr-CuCl catalyst can be reused at least 7 runs without significant decrease in its catalytic efficiency. ICP-OES, VSM and SEM techniques confirmed the recovered Fe3O4@BTH-Pyr-CuCl catalyst was very stable and had high magnetic property despite the utilization for 7 runs. [ABSTRACT FROM AUTHOR]

An unprecedented silver‐mediated intramolecular oxy‐argentation of 3‐amidoaryne precursors that quickly generates a heteroarylsilver species is developed. AgF acts as both a stoichiometric fluoride source and a reagent for the formation of a benzoxazolylsilver intermediate via aryne generation. Pd‐catalyzed coupling reactions of (hetero)aryl iodides with a silver species, generated in situ, allow for the synthesis of various C7‐arylated benzoxazoles. As a result, an aryl group is selectively introduced into the meta‐position of 3‐amidobenzyne precursors. Mechanistic studies have indicated the presence of a benzoxazolylsilver intermediate and revealed that the reaction proceeds via an intramolecular oxy‐argentation process, which is initiated by a direct fluoride attack on the silyl group. [ABSTRACT FROM AUTHOR]

An iron‐catalyzed Sonogashira coupling of non‐activated secondary alkyl iodides with terminal alkynes is described. The reaction proceeds under mild conditions in N‐MethylPyrrolidone without auxiliary ligand or co‐catalyst. This procedure allowed the obtention of 28 coupling products. Moreover, slow addition of LiHMDS base allows to achieve up to 89% yields. This method enables the conversion of non‐activated alkyl iodides in a Fe‐catalyzed Sonogashira‐type cross‐coupling, which was so far not achievable with iron catalysts. Preliminary mechanistic studies suggest the implication of a key single electron transfer in the catalytic process. [ABSTRACT FROM AUTHOR]

A general approach to the direct deoxygenative transformation of primary, secondary, and tertiary alcohols has been developed. It undergoes through phosphoranyl radical intermediates generated by the addition of exogenous iodine radical to trivalent alkoxylphosphanes. Since these alkoxylphosphanes are readily in situ obtained from alcohols and commercially available, inexpensive chlorodiphenylphosphine, a diverse range of alcohols with various functional groups can be utilized to proceed deoxygenative cross‐couplings with alkenes or aryl iodides. The selective transformation of polyhydroxy substrates and the rapid synthesis of complex organic molecules are also demonstrated with this method. [ABSTRACT FROM AUTHOR]

Aryl and heteroaryl iodides have been efficiently converted into the corresponding thioacetates in cyclopentyl methyl ether (CPME), a green solvent, under Cu catalysis. The chemoselectivity of the reaction is mainly controlled by electronic factors, enabling the conversion of both electron-rich and electron-deficient substrates into the corresponding thioacetates in good to excellent yields. The products can be easily deprotected to the corresponding thiolates to carry out additional synthetic transformations in situ. Surprisingly, despite CPME's relatively low dielectric constant, the reaction rate significantly increased when conducted under microwave irradiation conditions. This synthetic methodology exhibits a remarkable tolerance to functional groups, mild reaction conditions, and a wide substrate scope, utilizing a safe and inexpensive CuI pre-catalyst in the green solvent CPME. A non-aqueous workup allowing for the complete recovery of both catalyst and solvent makes this approach an environmentally sustainable protocol for C(sp2) sulfur functionalization. Additionally, the reaction shows selective cross-coupling with iodides in competition with chlorides and bromides, allowing its use in multistep syntheses. To demonstrate the potential of this methodology, it was applied to the high-yield synthesis of a photochromic dithienylethene, where a selective synthesis had not been reported before. [ABSTRACT FROM AUTHOR]

This article provides an overview of recent advancements in transition-metal-catalyzed Sonogashira cross-coupling reactions of alkyl electrophiles. It discusses the challenges associated with coupling nonactivated alkyl electrophiles and highlights three catalytic systems that have been developed to address these challenges. The article also mentions the development of enantioselective Sonogashira reactions using copper catalysts with chiral ligands. The challenges and future directions in this field are also discussed. [Extracted from the article]

Herein, we show that a photoCORM behaves as a highly substrate-tolerant, photoactivable in situ CO surrogate, allowing the synthesis of variously functionalised amides including the biologically active compound Moclobemide by Pd-catalysed aminocarbonylation between aryl iodides and amines under mild conditions. This work should bring about a useful input to the field of carbonylative transformations. [ABSTRACT FROM AUTHOR]