Search

Stereospecific approaches allow the introduction of a stereogenic center into complex organic molecules using optically active reagents. Among these, the Pd-catalyzed stereospecific cross-coupling of chiral alkylboron compounds stands out as a highly effective tool for organic synthesis. In parallel with advances in the development of borylation technology, the strategy has recently witnessed a growth in its applicability. This account aims to review the progress on Pd-catalyzed stereospecific B -alkyl Suzuki–Miyaura cross-coupling, tracing its evolution from early breakthroughs to the most recent advances. 1 Introduction 2 Cross-Coupling of 1° Alkylboron Compounds 3 Cross-Coupling of Benzylboron Compounds 4 Cross-Coupling of Allyl- and Propargylboron Compounds 5 Cross-Coupling of Other Types of Activated 2° Alkylboron Compounds 6 Cross-Coupling of Unactivated 2° Alkylboron Compounds 7 Conclusion and Outlook [ABSTRACT FROM AUTHOR]

The synchronization control of its dual hydraulic cylinder moving beam in fatigue testing machine requires robustness and high synchronization accuracy. The synchronization control accuracy is affected by the time-varying nonlinearity of parameters, mutual coupling and load disturbance of the multi-cylinder system affect. A novel control strategy with single-cylinder self-immunity and double-cylinder fuzzy single neuron is proposed to overcome the slow compensation response and poor robustness of dynamic adjustability. First the working principle of the moving beam synchronization system of the fatigue testing machine is described, then the mathematical simulation model of the asymmetric single and double cylinders and their synchronization control system are established to carry out the simulation analysis of the tracking performance and synchronization performance. Finally the experimental is setup to verify the simulation analysis. The results show that the designed synchronization controller can meet the application requirements of the fatigue testing machine moving beam extremely well. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Over the past few decades, N‐sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis, allowing for diverse innovative and original chemical transformations that were otherwise difficult to achieve. This critical review summarizes the major advancements in the carbene chemistry of N‐sulfonyl hydrazones. The contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this field. The individual carbene transfer reactions and their mechanisms, as well as the potential applications in the synthesis of natural products and complex bioactive molecules, are thoroughly discussed. [ABSTRACT FROM AUTHOR]

A new MOF (Co‐TIST) was synthesized from 2,4,6‐tris (imidazol‐1‐yl)‐1,3,5‐s‐triazine (TIST) and cobalt nitrate. TIST was prepared from the reaction of cyanuric chloride and imidazole and used as a ligand for the formation of MOF. After characterization of Co‐TIST by different methods, we have investigated the carbonyl‐Heck cross‐coupling reaction of aldehydes with aryl halides in the presence of Co‐TIST as a new heterogeneous catalyst. Various ketones were obtained in good to high yields by this method. The reactions did not require high temperature, additives, or large amounts of the catalyst. The catalyst was recycled in five consecutive runs with unimportant decrease in its catalytic activity. Notably, this is the first report of using a MOF for the carbonyl‐Heck cross‐coupling reaction of aryl halides and aldehydes. [ABSTRACT FROM AUTHOR]

This paper presents a tunable center frequency and small size cavity bandpass filter design method. In this method, a capacitor-loaded open terminal coaxial resonator is employed to reduce the size of cavity filters. The resonator is designed and fabricated separately into two parts to achieve the flexible operating frequency purpose. The first part is called the base of the resonator which is simply a pillar and directly fabricated integrally with the cavity housing. The second part called the hat of the resonator is the main part causing the load capacitance in cavity filters. By using different heights of the base part or/and different shapes and sizes of the hat, the operating frequency of cavity filters can be changed flexibly. This method not only reduces the difficulty and cost of cavity filter processing but also makes cavity filters reconfigurable. To demonstrate the effectiveness of the method, a cavity filter sample with a center frequency of 3.45 GHz and a bandwidth of 80 MHz was designed, fabricated, and measured. The measured results show that the insertion loss was smaller than 1.33 dB in the whole bandwidth, one zero-point at 3.350 GHz reaching -68 dB, the rejection at 3.550 GHz was -41 dB, unloaded Q was 5,898, and the dimension of the filter was 128 mm×86 mm×23 mm. [ABSTRACT FROM AUTHOR]

Cross‐coupling of nitriles and alcohols offers an environmentally friendly and atom‐economical method for the synthesis of various valuable compounds. These compounds include α‐alkylated and α‐olefinated nitriles, primary amines, imines, N‐alkylation amines, amides, N‐heterocycles, δ‐hydroxynitriles, olefins, etc. Herein, we have reviewed recent developments (from 2013–date) of transition‐metal‐catalyzed cross‐coupling of nitriles and alcohols. A number of transition metal complexes such as noble metals Ru and Ir, as well as base metals Mn, Fe, Co, and Ni are presented. Moreover, different product types, reaction conditions and mechanisms are discussed to understand the reaction and catalyst development. [ABSTRACT FROM AUTHOR]

We are reporting the preparation and use in cross‐coupling reactions of a newly developed, bench‐stable (1‐fluorocyclopropyl)metalloid reagent. The Stille cross‐coupling reaction described for this α‐fluorinated stannane reagent is amenable to a wide range of aryl and alkenyl (pseudo)halides bearing a variety of functional groups. An enantioenriched cross‐coupled product was also obtained from the corresponding 1‐fluorocyclopropyltin reagent bearing an ester handle. Finally, the chemical stability of the 1‐fluorocyclopropyl moiety was also demonstrated by performing several post‐functionalizations. [ABSTRACT FROM AUTHOR]

Herein, the use of economically and environmentally friendly bis(pinacolato)diboron (B2Pin2) is described as a non‐metallic reductant in mediating Ni‐catalyzed C(sp3)–C(sp2) reductive cross‐coupling of alkyl electrophiles with aryl/vinyl halides. This method exhibits excellent suitability for heteroaryl halides and alkyl halides/Katritzky salts. The present study is compatible with an in situ halogenation of alcohol method, allowing for selective mono‐functionalization of diols and bio‐relevant alcohols (e.g., carbohydrates). The use of B2Pin2 shows potential for easy scalability without introducing additional metal impurities into the products. It is observed for the first time in the realm of cross‐electrophile coupling chemistry that B2Pin2 can sever as a reductant to reduce NiII to Ni0. This mechanistic insight may inspire the development of new reductive bond‐forming methodologies that can otherwise be difficult to achieve with a metal reductant. [ABSTRACT FROM AUTHOR]

A highly effective oxidation cross-coupling method involving para -cresol derivatives and malononitrile derivatives has been developed utilizing undivided electrolytic conditions. This electrochemical approach offers a robust route for synthesizing diverse malononitrile derivatives featuring quaternary carbon centers and incorporating para -phenol groups. Notably, the direct electrooxidation of the C(sp3)–H bond in the para -cresol derivative plays a crucial role in this process under electrolytic conditions. Various para -cresol derivatives and malononitrile derivatives with different substituents are readily compatible with this electrochemical transformation, affording coupling compounds in up to 99% yield. [ABSTRACT FROM AUTHOR]

Cope rearrangements have garnered significant attention owing to their ability to undergo structural reorganization in stereoselective manner. While substantial advances have been achieved over decades, these rearrangements remained applicable exclusively to parent 1,5‐hexadienes. Herein, we disclose the gold‐catalyzed arylative Cope rearrangement of 1,6‐heptadienes via a cyclization‐induced [3,3]‐rearrangement employing ligand‐enabled gold redox catalysis. Detailed mechanistic investigations including several control experiments, cross‐over experiment, HRMS analysis, 31P NMR and DFT studies have been performed to underpin the mechanism. [ABSTRACT FROM AUTHOR]

gem‐Diborylalkanes are highly valuable building blocks in organic synthesis and pharmaceutical chemistry due to their ability to participate in multi‐step cross‐coupling transformations, allowing for the rapid generation of molecular complexity. While progress has been made in their synthetic metholodology, the construction of β‐tertiary and C(sp3)‐rich gem‐diborylalkanes remains a synthetic challenge due to substrate limitations and steric hindrance issues. An approach is presented that utilizes synergistic photoredox and copper catalysis to achieve efficient C(sp3)−C(sp3) cross‐coupling of alkyl N‐hydroxyphthalimide esters, which can easily be obtained from alkyl carboxylic acids, with diborylmethyl species, providing a series of C(sp3)‐rich gem‐diborylalkanes with 1°, 2°, and even 3° β positions. Furthermore, this approach can also be applied to complex medicinal compounds and natural products, offering rapid access to molecular complexity and late‐stage functionalization of C(sp3)‐rich drug candidates. Mechanistic experiments revealed that diborylmethyl Cu(I) species participated in both the photoredox process and the key C(sp3)−C(sp3) bond‐forming step. [ABSTRACT FROM AUTHOR]

Transition metal‐catalyzed cross‐coupling reactions have become a powerful and widely used synthetic approach for the construction of both carbon‐carbon and carbon‐heteroatom bonds. These reactions have revolutionized synthetic chemistry by enabling the efficient formation of complex molecular architectures. Among the various methods available, the bimolecular homolytic substitution (SH2) reaction has emerged as an attractive and versatile method for the formation of C(sp3)−C(sp3) and C(sp3)‐heteroatom bonds. In recent years, significant progress has been made in the development of radical SH2 reactions, particularly those involving different transition metal complexes such as cobalt, nickel, and iron. These advancements have expanded the scope of SH2 reactions, allowing for greater diversity in substrate compatibility and reaction conditions. In this review, we aim to highlight the latest breakthroughs and mechanistic insights into radical SH2 reactions, focusing on the role of transition metal catalysts in facilitating these transformations. We will discuss the various types of transition metal complexes that have been employed, the mechanistic pathways involved, and the potential applications of these reactions in the synthesis of complex organic molecules. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Recent advances in transition metal‐catalyzed o‐carborane B—H activation have led to the rapid development of various methodologies for cage boron functionalization. For catalytic cage B—H acyloxylation, intermolecular oxygenation gave products with different regioselectivities (B(3)‐, B(4)‐, and B(8,9)‐selectivities). Herein, an efficient palladium‐catalyzed direct cage B(4)–H oxygenation of o‐carboranylacetic acids has been achieved, where the carboxylic group serves as not only a directing group, but also a coupling partner. A wide range of substituted o‐carboranylacetic acids have been cyclized via the formation of B(4)−O bond to give the corresponding γ‐lactones in modest to excellent yields. A Pd(IV) intermediate is proposed to be involved in the catalytic cycle. This work offers valuable references for the BH/OH dehydrocoupling reactions under mild conditions to produce carborane‐featuring functional molecules. [ABSTRACT FROM AUTHOR]

Indan‐1,3‐diones stand as versatile precursors to a plethora of complex molecules with wide applications; however, their direct cross‐coupling methodologies remain largely unexplored. Herein, we unveil an in situ triflation‐tandem cross‐coupling strategy to synthesize a diverse variety of indenones and benzofulvenes from indan‐1,3‐diones. The successful synthesis of a neolignan natural product and the key intermediate of Indatraline (antidepressant) showcased the synthetic utility of the methodology. The strategy enabled tuning the electronic characteristics of indenones and benzofulvenes, modulating the HOMO‐LUMO gaps. The photophysical properties of these molecules were studied, and the experimental results were compared with the predictions obtained from the DFT studies. [ABSTRACT FROM AUTHOR]

Despite the paramount importance of the Suzuki–Miyaura coupling (SMC) in academia and industry, and the great promise of iron to offer sustainable catalysis, iron‐catalyzed SMC involving sp3‐hybridized partners is still in its infancy. We herein report the development of a versatile, well‐defined electron‐deficient anilido‐aldimine iron(II) catalyst. This catalyst effectively performed C(sp3)−C(sp2) and C(sp3)−C(sp3) SMC of alkyl halide electrophiles and (hetero)aryl boronic ester and alkyl borane nucleophiles respectively, in the presence of a lithium amide base. These couplings operated under mild reaction conditions and displayed wide functional group compatibility including various medicinally relevant N‐, O‐ and S‐based heterocycles. They also tolerated primary, secondary and tertiary alkyl halides (Br, Cl, I), electron‐neutral, ‐rich and ‐poor boronic esters and primary and secondary alkyl boranes. Our methodology could be directly and efficiently applied to synthesize key intermediates relevant to pharmaceuticals and a potential drug candidate. For C(sp3)−C(sp2) couplings, radical probe experiments militated in favor of a carbon‐centered radical derived from the electrophile. At the same time, reactions run with a pre‐formed activated boron nucleophile coupled to competition experiments supported the involvement of neutral, rather than an anionic, (hetero)aryl boronic ester in the key transmetalation step. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A novel electrochemical multicomponent cascade reaction of indole‐tethered alkenes with CF3SO2Na and n‐Bu4NI has been developed, which enables the rapid assembly of spiropyrrolidinyl‐oxindoles in good yields. The experimental results and DFT calculations suggest that this reaction proceeds through the oxidation of CF3SO2Na, radical coupling with alkene, spirocyclization, oxidation of sulfinate, iodide substitution, and water coupling. This strategy features mild reaction conditions, easy‐to‐handle reactants, and good chemical yields. This finding not only enriches the research contents of indole‐tethered alkenes but also provides a green strategy for the construction of spiropyrrolidinyl‐oxindoles compared with the existing methodologies. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Chemodivergent synthesis of benzofurans and 2,3‐dihydrobenzofurans has been realized. Under a reaction system consisting of DBDMH and K2CO3 as promotors, controlled conditions enabled the formation of two sets of valuable heterocycles from the tandem transformation of enaminones and salicylaldehydes. The key to success was the identification of the reaction parameters, in which the imine intermediate which was formed by transient halogenation coupling and substitution processes underwent either aldol condensation/annulation or imine hydrolysis/aldol condensation. The additives NH4Cl or Fe2(SO4)3 controlled the unique selectivity of this reaction. A broad substrate scope of enaminones and salicylaldehydes has been employed in this reaction, demonstrating excellent functional group tolerance and versatility. [ABSTRACT FROM AUTHOR]

Chalcones are a class of naturally occurring flavonoid compounds associated to a variety of biological and pharmacological properties. Several reviews have been published describing the synthesis and biological properties of a vast array of analogues. However, overviews on the reactivity of chalcones has only been explored in a few accounts. To fill this gap, a systematic survey on the most recent developments in the transition metal‐catalyzed transformation of chalcones was performed. The chemistry of copper, palladium, zinc, iron, manganese, nickel, ruthenium, cobalt, rhodium, iridium, silver, indium, gold, titanium, platinum, among others, as versatile catalysts will be highlighted, covering the literature from year 2000 to 2023, in more than 380 publications. [ABSTRACT FROM AUTHOR]

Nucleophilic fluorination of aromatic rings can be done via a cross-coupling reaction catalyzed by palladium and biaryl monophosphine ligands such as AlPhos. Nevertheless, aromatic fluorination via palladium catalysis can lead to regioisomers, a serious problem for this kind of reaction. An ortho-deprotonation mechanism was proposed for this reaction in previous studies. However, this mechanism does not explain why the ortho product is not formed from para and meta substrates, and the details of the mechanism are not fully understood yet. This theoretical work discloses the mechanism behind regioisomers formation, which takes place via unimolecular ortho-elimination of HF. The computed free energy profile of the reaction was followed by a detailed microkinetic analysis, which explain the experiments quantitatively. The present study shows that the rotation of the aryne coordinated to the palladium to form a complex leading to the ortho product is critical for regioselectivity. This rotation has a high free energy barrier due to steric repulsion with the adamantane group of the ligand. Such a feature impedes the formation of ortho product from para and meta substrates and allows the formation of the ortho product selectively from the ortho substrate. [ABSTRACT FROM AUTHOR]

Over the decades, conventional techniques have been reported for the direct conversion of a substantial framework of adamantyl C(sp3)‐H/Br/COOH bonds to various C−C, C−N, and other C−X bonds enabled by various catalytic conditions and reagents. There are various simple and direct methods for converting adamantane tertiary and secondary C‐(Sp3)‐H/X/M bonds to quaternary/ tertiary carbon‐carbon bonds that have been reported in previous years, which include methods such as catalytic approaches, cross‐coupling reactions, C−H bond functionalization, radical reactions, organometallics, and dual catalysis, etc. The selective catalytic techniques published between 2010 and 2023 are covered in this article. These adamantane derivatives are broadly studied in various fields such as medicinal chemistry applications, drug development, supramolecular chemistry, material science, catalysts/ligands, and nanotechnologies. [ABSTRACT FROM AUTHOR]

β‐Phenethylamines are widely represented in biologically and pharmacologically active organic small molecules. Here, we introduce N‐pyridinium aziridines as latent dual electrophiles for the synthesis of β‐phenethylamines. Bromide‐promoted ring opening generates β‐halopyridinium amines. Selective Ni‐catalyzed C−C cross‐coupling between organozinc nucleophiles and the benzylic C−Br electrophile affords a diverse family of β‐functionalized phenethylaminopyridinium salts, and coupling is stereoconvergent in the presence of chiral ligands. Subsequent Ni‐catalyzed reductive N−N bond activation within the β‐functionalized phenethylaminopyridinium salts furnishes the products of formal olefin carboamination. Other reductive N−N cleavage reactions are demonstrated to provide access to free primary amines, alkylated amines, heterocycles, and products derived from N‐centered radical chemistry. The developed reaction sequence can be implemented in the context of complex molecules and natural product derivatives. Together, the described results provide a general and modular synthesis of β‐phenethylamines and significantly expand the utility of N‐pyridinium aziridines as linchpins in chemical synthesis. [ABSTRACT FROM AUTHOR]

In this work, through the Suzuki–Miyaura cross-coupling reaction with high yields, new π-conjugated azulene compounds containing diphenylaniline groups at positions 2 and 6 of azulene were synthesized. The obtained diphenylaniline–azulenes have intensely visible-light absorbing and emitting (in the wavelength range from 400 to 600 nm) properties. It has been shown that such unique optical properties, in particular fluorescent emission in the region of blue and green photoluminescence (λem at 495 and 525 nm), which were absent in the original azulene, are the result of the electron donor effect of diphenylaniline groups, which significantly changes the electronic structure of azulene and leads to the allowed HOMO → LUMO electron transition. [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]

Comprehensive SummaryThe EDA complex‐mediated reactions involving oxime esters have been few studied. Herein, an EDA complex formed by thiophenolate anion and oxime ester is reported for photoinduced divergent synthesis of thioethers, depending on different types of oxime esters. Operational simplicity, mild reaction conditions, and flexible options of leaving group demonstrate the generality and synthetic utility of this approach. Such an approach can also enable an interesting thiol‐catalysis for the synthesis of phenanthridines. [ABSTRACT FROM AUTHOR]

We report the stepwise synthesis of a novel series of heterometallic gold(I)/palladium(II) complexes supported by heteroditopic imidazol‐2‐ylidene/triazol‐5‐ylidene ligands. All new compounds were characterized by means of 1H and 13C NMR spectroscopy, melting points, and elemental analyses. The versatility of the ligand platforms, additionally allows for the preparation of cationic chelate biscarbenic palladium(II) complexes through full deprotonation of the mixed azolium precursors. Characterization studies were completed by the determination of the molecular structures of some synthetic intermediates. The new biscarbenic palladium(II) complexes were tested as catalysts in the cross‐coupling of boronic acid to a variety of chloroarenes and the hydrosilylation of terminal alkynes. Both catalytic processes provide good to excellent yields under low catalyst loadings. [ABSTRACT FROM AUTHOR]

This review introduces the synthetic organic chemical value of α‐bromocarbonyl compounds with tertiary carbons. This α‐bromocarbonyl compound with a tertiary carbon has been used primarily only as a radical initiator in atom transfer radical polymerization (ATRP) reactions. However, with the recent development of photo‐radical reactions (around 2010), research on the use of α‐bromocarbonyl compounds as tertiary alkyl radical precursors became popular (around 2012). As more examples were reported, α‐bromocarbonyl compounds were studied not only as radicals but also for their applications in organometallic and ionic reactions. That is, α‐bromocarbonyl compounds act as nucleophiles as well as electrophiles. The carbonyl group of α‐bromocarbonyl compounds is also attractive because it allows the skeleton to be converted after the reaction, and it is being applied to total synthesis. In our survey until 2022, α‐bromocarbonyl compounds can be used to perform a full range of reactions necessary for organic synthesis, including multi‐component reactions, cross‐coupling, substitution, cyclization, rearrangement, stereospecific reactions, asymmetric reactions. α‐Bromocarbonyl compounds have created a new trend in tertiary alkylation, which until then had limited reaction patterns in organic synthesis. This review focuses on how α‐bromocarbonyl compounds can be used in synthetic organic chemistry. [ABSTRACT FROM AUTHOR]

Comprehensive Summary We herein describe a Cp*RhIII‐catalyzed C(sp3)–H mono‐arylation of 8‐methylquinolines with benign arylsilanes. The use of 1‐adamantane carboxylic acid can benefit the efficiency in this transformation, and AgF was both activator and reoxidant. Control experiments indicated inability of C—H cleavage in determining the rate of the reaction. [ABSTRACT FROM AUTHOR]

Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis are difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ and stereoselectivity, enabling the predictable and efficient synthesis of stereodefined alkenes. In fact, an appealing alternative approach for accessing challenging stereodefined alkene molecular frameworks could involve the sequential selective activation and cross‐coupling of strong bonds instead of conventional C−C bond formation. In this study, we introduce a series of programmed site‐ and stereoselective strategies that capitalizes on the versatile reactivity of readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through a tandem cross‐coupling reaction, which is catalyzed by an organometallic Rh‐complex to produce complex molecular scaffolds. By merging selective C−B and remote C−H bond functionalization, we achieve the in situ generation of polyfunctional C(sp2)‐nucleophilic intermediates. These species can be further modified by selective coupling reactions with various C‐based electrophiles, enabling the formation of C(sp2)−C(sp3) bond for the generation of even more complex molecular architectures using the readily available starting polyborylated‐alkenes. Mechanistic and computational studies provide insight into the origins of the stereoselectivities and C−H activation via a 1,4‐Rh migration process. [ABSTRACT FROM AUTHOR]

Quaternary carbons are embedded in various natural products, pharmaceuticals, and organic materials. However, constructing this valuable motif is far from trivial. Conventional approaches mainly rely on classical polar disconnections and encounter bottlenecks concerning harsh conditions, functional group tolerance, regioselectivity, and step economy. In this context, Kawamata, Baran, Shenvi, and co‐workers recently demonstrated that two feedstock chemicals, alkyl carboxylic acids and olefins, could be utilized to construct tetrasubstituted carbons in the presence of an inexpensive iron porphyrin catalyst and a suitable reductant combination through quaternization of the radical intermediates. The method enables access to various sterically encumbered quaternary carbons under mild and robust conditions. Taking a complete detour from conventional approaches, the present heteroselective radical–radical coupling simplifies the synthesis of quaternary carbon‐containing molecules through an innovative and distinctive disconnection approach. [ABSTRACT FROM AUTHOR]

With halogen‐atom transfer as an effective tool, a novel catalytic enantioselective protocol to generate chiral trifluoromethylated alkynes has been established by a cooperative photoredox and nickel catalysis system, providing a straightforward and modular route to access this type of product in good yields and enantioselectivities. The halogen‐atom transfer process is essential for the reaction and this novel strategy offers another promising way to utilize alkyl halides with highly negative reduction potentials. It firstly expands nickel‐catalyzed asymmetric reductive cross‐couplings of organohalides from the traditional single‐electron transfer to halogen‐atom transfer. [ABSTRACT FROM AUTHOR]

Aryl bromides and 4‐chlorotoluene as an example aryl chloride in the presence of N‐heterocyclic carbene (NHC) palladium hydroxo dimers of the type [{Pd(μ‐OH)Cl(NHC)}2] (where NHC=IPr, SIPr, IMes, SIMes) undergo an efficient and selective Sonogashira cross‐coupling with (hetero)arylacetylenes. The procedure allows the high‐throughput and selective synthesis of a broad spectrum of 1,2‐diarylacetylenes using 10 ppm of [{Pd(μ‐OH)Cl(IPr)}2] as precatalyst. For the coupling of 4‐chlorotoluene with phenylacetylene, TON=560000 was achieved. Hydrogen chloride was observed as a product of the Sonogashira cross‐coupling reaction. The formation of the active Pd(0) from the Pd(II) complex was found to proceed via ethanol oxidation. Mechanistic studies showed that water plays a key role in the reaction. [ABSTRACT FROM AUTHOR]

A direct α‐alkenylation of nitrile compounds was realized with a palladium complex. This method exhibited excellent tolerance toward a variety of α‐aryl alkyl nitriles and vinyl bromides, leading to the formation of a series of α‐quaternary nitriles containing vinyl groups. Further manipulations of the obtained products were demonstrated, highlighting the potential synthetic utility of this method. [ABSTRACT FROM AUTHOR]

Over the years, polynuclear cyclic or torus complexes have attracted increasing interest due to their unique metal topologies and properties. However, the isolation of polynuclear cyclic organometallic complexes is extremely challenging due to their inherent reactivity, which stems from the labile and reactive metal‐carbon bonds. In this study, the pyrazine ligand undergoes a radical‐radical cross‐coupling reaction leading to the formation of a decanuclear [(Cp*)20Dy10(L1)10] ⋅ 12(C7H8) (1; where L1 = anion of 2‐prop‐2‐enyl‐2H‐pyrazine; Cp* = pentamethylcyclopentadienyl) complex, where all DyIII metal centres are bridged by the anionic L1 ligand. Amongst the family of polynuclear Ln organometallic complexes bearing CpR2Lnx units (CpR = substituted cyclopentadienyl), 1 features the highest nuclearity obtained to date. In‐depth computational studies were conducted to elucidate the proposed reaction mechanism and formation of L1, while probing of the magnetic properties of 1, revealed slow magnetic relaxation upon application of a static dc field. [ABSTRACT FROM AUTHOR]

There is a pressing need for methods that can connect enantioenriched organic compounds with readily accessible building blocks via asymmetric functionalization of unreactive chemical bonds in organic synthesis and medicinal chemistry. Herein, the asymmetric chemoselective cleavage of two unactivated C(Ar)−O bonds in the same molecule is disclosed for the first time through an unusual nickel‐catalyzed carbomagnesiation. This reaction facilitates the evolution of a novel atroposelective ring‐opening difunctionalization. Utilizing readily available dibenzo bicyclic substrates, diverse valuable axially chiral biaryls are furnished with high efficiencies. Synthetic elaborations showcase the application potential of this method. The features of this method include good atom‐economy, multiple roles of the nucleophile, and a simple catalytic system that enables the precise magnesiation of an α‐C(Ar)−O bond and arylation of a β‐C(Ar)−O bond. [ABSTRACT FROM AUTHOR]

A general and convenient selective direct arylation of the 3‐position of triimidazo[1,2‐a:1',2'‐c:1",2"‐e][1,3,5]triazine (1) with (hetero)aryl halides in DMA was successfully achieved in the presence of K2CO3 as the base and a catalyst precursor consisting of Pd(OAc)2 and P(2‐furyl)3. Electron‐poor and ‐rich (hetero)aryl moieties, including the strongly deactivated and sterically encumbered 2,4,6‐trimethoxyphenyl unit, are well tolerated in the electrophilic partner. The data obtained in this synthetic study support a reaction mechanism involving an electrophilic attack of an arylpalladium‐(II) halide species onto the triazine ring. [ABSTRACT FROM AUTHOR]

The realm of application of organometallic catalysis to organic synthesis has witnessed a transformative shift in recent years, owing much to the evolution of ate complexes from mere reagents to versatile catalysts. Ate complexes, formed through the coordination of a neutral Lewis acid with an organic anionic base, have emerged as pivotal intermediates that not only facilitate organic transformations but also serve as efficient catalysts in a wide range of chemical reactions. This review presents the fascinating journey of ate complexes, highlighting their development from stoichiometric reagents to active catalysts. Historically, ate complexes were primarily regarded as stoichiometric species essential for various metal-catalyzed transformations. However, constant research has unveiled their potential as catalysts in their own right, reshaping the landscape of modern organic synthesis. In this minireview, we discuss the pivotal role of ate complexes in the evolution of organic synthesis, from their early days as reactive intermediates to their current stature as catalytic pioneers offering a glimpse into the exciting future of this dynamic field.

In the past few decades, transition-metal-catalyzed direct amination of aryl halides with ammonia has attracted significant attention from chemists because of its broad substrate scope, good functional group compatibility, and high reaction selectivity. Herein, recent examples of transition-metal-catalyzed syntheses of aniline derivatives starting from aryl halides are reviewed. 1 Introduction 2 Heat-Driven Transition-Metal-Catalyzed Amination of Aryl Electrophiles 2.1 Palladium-Catalyzed Amination 2.2 Copper-Catalyzed Amination 2.3 Nickel-Catalyzed Amination 3 Light-Driven Transition-Metal-Catalyzed Amination of Aryl Electrophiles 4 Conclusion and Outlook [ABSTRACT FROM AUTHOR]

A stereoselective N-alkenylation of azoles with alkynes and iodine(III) electrophile is reported. The reaction between various azoles and internal alkynes is mediated by benziodoxole triflate as the electrophile in a trans-fashion, affording azole-bearing vinylbenziodoxoles in moderate to good yields. The tolerable azole nuclei include pyrazole, indazole, 1,2,3-triazole, benzotriazole, and tetrazole. The iodanyl group in the product can be leveraged as a versatile synthetic handle, allowing for the preparation of hitherto inaccessible types of densely functionalized N-vinylazoles.

The development of a new and straightforward chemoselective method for the synthesis of uracil-based structures by combining Suzuki–Miyaura and Sonogashira–Hagihara cross-coupling is reported. The methodology was applied to synthesize a series of novel compounds. The tolerance of the combination of different functional groups was tested. The influence of different functional groups on the physical properties was studied by ultraviolet–visible (UV–vis) and fluorescence spectroscopy, providing new insights into the potential applications of uracil-based structures.

Phenol derivatives are naturally abundant or can be easily fabricated from commercially accessible building blocks. In recent years, with the aim of producing functionally important chiral compounds in enantioenriched form, there has been initial progress in the development of metal‐catalyzed cross‐coupling reactions that involve the enantioselective cleavage of aromatic C−O bonds. This concept encompasses a review of the significant advancements in this field, as well as the associated strategies. Moreover, the challenges and potential opportunities in this area are also underscored. [ABSTRACT FROM AUTHOR]

We report an unprecedented Ni‐catalyzed direct monofluoromethylthiolation of acyl chlorides, in situ generated from carboxylic acids, with elemental sulfur (S8) as the S source and fluoroiodomethane (ICH2F) as the CH2F radical source to produce a series of monofluoromethylthioesters in moderate to good yields. This approach features excellent functional group tolerance and broad substrate scope. Additionally, the late‐stage monofluoromethylthiolation of complex bioactive molecules can also be accomplished using this method. [ABSTRACT FROM AUTHOR]

Non‐directed regioselective activation of bis(boronic esters), followed by functionalization, is reported. A bulky activator is shown to selectively activate the less hindered boronic ester enabling it to undergo stereospecific cross‐coupling to a variety of electrophiles. This steric‐based regioselectivity provides a simple and efficient method to prepare highly functionalized, enantiomerically enriched products starting from simple alkenes. [ABSTRACT FROM AUTHOR]

Comprehensive Summary Key Scientists The construction of acyclic quaternary carbon stereocenters, which are ubiquitous in many bioactive compounds, pharmaceuticals and natural products, has been a long persuit in synthetic organic chemistry. Among numerous methods, enantioselective nickel‐catalysis has attracted incremental attention in recent years. This review summarizes the recent development in the asymmetric strategies, research progress, mechanistic investigations for the generation of acyclic quaternary carbon stereocenters via enantioselective nickel catalysis.In 2006, the Zhou group and RajanBabu group realized the nickel‐catalyzed enantioselective hydrovinylation of α‐substituted styrenes and ethylene to construct acyclic quaternary carbon stereocenters (QCSs) by using spiro‐ and binaphthyl phosphoramidite ligands, respectively. In 2016, Watson developed a nickel‐catalyzed Suzuki‐Miyaura arylation to generate acyclic QCSs via chirality transfer reaction. In 2017, the Feng and the Fu group developed nickel‐catalyzed enantioselective conjugated/Michael additions to build acyclic QCSs, respectively. In 2020, the Fang group made the first success in the construction of QCSs by nickel‐catalyzed hydrocyanation of alkenes and allenes. In 2021, Gregory C. Fu and co‐workers disclosed a nickel‐catalyzed enantioselective α‐functionalization of carbonyl compounds that could form acyclic QCSs. At the same time, the Shi group constructed chiral acyclic QCSs via nickel‐catalyzed functionalization of alkenes. In 2023, Kleij and co‐workers applied a new strategy for Ni‐catalyzed regio‐ and enantioselective homoallylic coupling to construct acyclic QCSs. In the same year, Tao and co‐workers demonstrated a novel strategy that is dinickel‐catalyzed enantioselective α‐alkylation of carbonyl compounds with alkyl iodides. [ABSTRACT FROM AUTHOR]

A method for the silver(I)‐catalyzed phosphonation of electron‐deficient 2‐arylbenzo[d]thiazoles has been developed. This strategy is highly regioselective for obtaining para‐selective phosphonation products by cross‐dehydrogenation coupling with good functional group tolerance and requires no prefunctionalization. This facile approach provides a practical route for synthesizing arylphosphine oxides. Mechanistic studies show that the para‐phosphonation occurs via a radical process. [ABSTRACT FROM AUTHOR]

In this study, we have developed a metal‐mediated synthetic method for incorporating the 1,1,2,2‐tetrafluoroethyl (CF2CF2H) motif into unactivated, electron‐rich alkenyl iodides using cross‐coupling reactions. We discovered that the stable Cu(CF2CF2H)(PPh2Me)3 complex, while unreactive with these substrates, serves as a P‐ligated reservoir for the formation of solvent‐stabilized "ligandless" and reactive CuCF2CF2H species. This transformation occurs upon addition of CuBr, which partially scavenges the P‐ligand in the form of CuBr(PPh2Me)3. The resulting in situ generated solvent stabilized "ligandless" system significantly enhances the reactivity of the complex, particularly towards challenging electron‐rich substrates. This advancement enables the synthesis of HCF2CF2‐glycals, as well as nucleosides/nucleobases and arenes. [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]

Comprehensive Summary: The conversion of CF3‐alkenes to gem‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work, a concise construction of gem‐difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: An asymmetric synthesis of dihydrospirotryprostatin B was achieved in 15 steps (8 purifications) from L‐tryptophan. The main feature of our synthetic strategy is the efficient construction of spirocyclic oxindole intermediate containing a chiral quaternary carbon center, involving the silica gel‐mediated cyclization of tryptamine‐ynamide and oxidation under neat conditions. [ABSTRACT FROM AUTHOR]

The use of Pd‐catalysts based on biaryl phosphacycles allowed facile Suzuki‐Miyaura couplings of a wide range of deactivated, sterically hindered, and heteroaryl chloride substrates with aryl boronic acids. Notably, the strongly electron‐deficient and sufficiently hindered biaryl phosphacycle ligand 7 consistently demonstrated effective performance. [ABSTRACT FROM AUTHOR]