This comprehensive review summarizes the published literature data concerning the chemistry of α‐enolazible alkynones, also denoted aliphatic or C‐H active alkynones, where an alkyl group is adjacent to the carbonyl function, from the first example in 1949 to the present day. Starting from a historical perspective, the reader will be introduced to the recent achievements and future challenges in this

Catalytic dearomatization of arenols is an uphill task that can serve as a powerful method to construct C‐C bonds with unsaturated coupling partners. Herein, a simple and efficient strategy for coupling naphthols with allylic alcohols is reported. A single Ru(II) pincer catalyzed coupling of naphthols with primary allylic alcohols led to the formation of benzo(f)chromanes, whereas the use of secondary

Difuropyridines have been prepared from aldehydes and chitin‐derived 3‐acetamidofuran (3AF) under acid‐catalyzed conditions. Difuropyridines were comprehensively synthesized for the first time. The synthesized difuropyridines can be applied to prepare fluorescent probe analogs or catalyze decarboxylative reactions as photocatalysts.

An efficient Rh(III)‐catalyzed C‐H bond activation/cyclization of 2‐arylbenzimidazoles with CF3‐imidoyl sulfoxonium ylides has been achieved, yielding diverse CF3‐ and amino‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines, which could undergo a deaminative hydroxylation to access CF3‐ and hydroxy‐disubstituted 5,6‐dihydrobenzoimidazo[2,1‐a]isoquinolines under Sc(OTf)3 catalyst. This developed

The bicyclo[3.3.1]nonane ring represents an attractive yet challenging synthetic targets in the field of organic synthesis, especially in a stereocontrolled fashion. Over the past two decades, organocatalysis has emerged as an enabling technology for the facile construction of enantioenriched molecules with remarkably increasing complexity and diversity, and a myriad of chiral architectures containing

A concise and practical sustainable strategy for modular access to isoquinoline‐fused benzo[f][1,3]oxazepine derivatives through a formal [4+3] annulation of commercially available salicyaldehydes with isoquinolinium salts has been developed. The reactions proceeded through the formation of two new bonds (C=C and C‐O) and a seven‐membered heterocyclic ring in one pot. Remarkably, use of simple NaHCO3

We have developed a synthesis for tetrahydro‐β‐carbolines involving cascade sigmatropic rearrangements. The substrates were conveniently prepared from parent anilines via a [2,3]‐sigmatropic rearrangement and cyanomethylation. Silver‐mediated decyanation afforded the corresponding iminium cation, which underwent a cascade consisting of an aza‐Cope rearrangement, an aza‐oxa‐Cope rearrangement, an aromatization

A copper‐catalyzed carbo‐/protoboration of boryl enynes is disclosed, providing access to an array of penta‐ and hexasubstituted diboryl dienes in a chemo‐, regio‐ and stereoselective manner. All six positions of the dienes can be manipulated using this methodology. The hexasubstituted diene boronates adopt a skew conformation. An iterative Suzuki coupling of the products provided highly conjugated

Merging the stereoisomeric mixture of substrate into a single product through stereospecific transformation is a challenging but higher‐order synthetic strategy, which perfectly meets the demand of cost control in the precise chemical production. In this work, the stereoconvergent synthesis of Z‐allylic boronates was realized with protoborylation of E/Z‐mixed 1,3‐dienes catalyzed by a novel copper‐guanidine

The asymmetric transfer hydrogenation of 3‐substituted 2H‐1,4‐benzoxazines with an azeotropic mixture of HCO2H/NEt3 (5/2) using tethered Cp*Rh(III)‐diamine catalysis has been realized. This process allows access to a broad range of chiral 3,4‐dihydro‐2H‐1,4‐benzoxazines in high yields with up to 99% ee, and tolerates a variety of functional groups. The enantiocontrol is achieved by the judicious choice

Diaryl and heteroaryl ethers are important and common motifs in drug discovery and agrochemicals. Here we present a catalytic system for the copper catalysed arylation of phenols with aryl halides. Bidentate N‐heterocyclic carbene ligands provide a well‐defined catalytic system that enable low loading of copper in effective coupling reactions (0.5 mol% Cu or lower). The reaction scope of aryl iodides

Benzylidene imidazolones with an ortho‐sec‐amino group undergo chemodivergent photochemical transformations, based on the wavelength of irradiation. Irradiation at 525 nm causes dimerization and the formation of cyclobutanes with two spiroatoms, related to dictazoles in 87‐98% yields. In turn, irradiation at 365 nm provides access to spirocyclic indolines in 67‐92% yields. Each of the processes proceeds

A gold(I)‐catalyzed regioselective cycloisomerization of bis(indol‐3‐yl)‐ynamides for the rapid construction of five‐membered ring linked bisindole derivatives has been reported, affording the desired products in the range of 72% ‐ 94% yields under mild conditions along with broad substrate scope. Moreover, DFT calculation of the NBO (natural bond orbital) charge supports the origin of its regioselectivity

Herein, we report the development of photoredox‐catalyzed N−H insertion of sulfoxonium ylides with amines via oxidative single‐electron transfer (SET). These reactions exhibit broad substrate scope (32 examples) and offer operationally simple, scalable procedures for accessing α‐ketoamides in a single step. Mechanistic studies and control experiments confirm the participation of a photogenerated carbon

An environmentally benign route for the synthesis of sulfonamides via Sulfur (VI) Fluoride Exchange (SuFEx) chemistry utilizing N‐methylimidazole, that simultaneously act as a base, precatalyst, HF by‐product scavenger, as well as solvent, is described. This one‐step sulfonamide synthesis exhibits excellent reactivity toward highly electron‐deficient and less nucleophilic anilines as well as aminopyridines

Herein, an electroreductive aryl radical enabled 5‐exo‐dig cyclization of N‐cyano‐2‐halobenzamides is presented, providing a convenient route for the synthesis of a variety of 3‐iminoisoindolin‐1‐ones in 30–75% yields. Simply by employing zinc plate instead of graphite rod anode, the products of the electrosynthesis are switched to diverse 3‐aminoisoindolin‐1‐ones through aryl‐radical‐mediated 5‐exo‐dig

The Perylene diimide (PDI) is an underexplored synthetic organic dye with significant potential in photoredox catalysis. We have developed a good chemo‐ and regioselective, atom‐economical methodology for synthesizing trifluoroethylated saturated heterocyclic derivatives and trifluoroethyl‐containing cyclobutane derivatives. This process involves the generation of trifluoromethyl radical from the Langlois

Herein, we report an efficient approach to synthesizing hybrid 3‐spiropiperidines heterocycles that incorporate both 3‐isochromanone and 3‐isoindolinone units through a one‐pot, double cascade reaction facilitated by an economical K₂CO₃/TBAB catalytic system. By examining the nucleophilicity of the lactone 3‐isochromanone, we developed a cascade reaction pathway that first generates a bi‐nucleophilic

Described herein is the discovery of a palladium‐catalyzed chlorocylization strategy for the synthesis of 3‑chloroindoles tolerated with a wide range of functional groups in moderate to excellent yields. In this transformation, the solvent effect is so important that only THF presents the positive effect. Furthermore, the present method provides an essay access to the N‐unprotected 3‐chloroindoles

We present a novel and highly efficient method for synthesizing polyfunctionalized 1,2,4‐triazoles. This approach leverages visible light and arylazo sulfones in combination with N‐vinyl amides, in the environmentally friendly solvent ethyl acetate. Remarkably, the reaction proceeds without the need for (photo)catalysts, ensuring near‐perfect atom economy and producing only water as a by‐product. This

Herein, we introduce a novel method for the synthesis of S‐substituted isothiourea compounds via the selective 1,2‐carboimination between oxime esters as bifunctional reagents and the C=S bond of isothiocyanates under visible‐light catalysis. This approach deviates from conventional methods by precisely modulating the substrate electronics to selectively functionalize the C=S bond of isothiocyanates

The asymmetric transfer hydrogenation of various dibenzo‐fused azepines including 5H‐dibenzo[b,e][1,4]diazepines, dibenzo[b,f][1,4]thiazepines and 11H‐dibenzo[b,e]azepines using chiral iridium diamine catalysts and HCO2H/NEt3 as the hydrogen source has been accomplished. A rang of chiral 10,11‐dihydro‐5H‐dibenzo[b,e][1,4]diazepines, 10,11‐dihydrodibenzo[b,f][1,4]thiazepine and 6,11‐dihydro‐5H‐dibenzo[b

A six‐membered ring bromo‐etherification of ε‐alkenyl alcohols using N‐oxide catalyst was developed to furnish 2‐bromomethyl‐6‐substituted tetrahydropyrans with cis‐selectivity and 3‐bromomethyl isochromans in high yields. DFT calculations indicate that the NMO catalyst enhances the electrophilicity of the bromine atom on NBS via two hydrogen‐bonding interactions after the formation of the NMO‐NBS

. Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant‐free conditions. Our straightforward carbonylative strategy enables access to versatile α,β‐unsaturated γ‐lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas as starting materials. The employment

The selective N‐C bond cleavage of amides to create value‐added products through a transition metal‐free approach has become a significant challenge. Here, we present a method to convert amides into N‐(3‐acylamidopropyl)lactams through sequential amide chemoselective N‐C bond cleavage and amidine ring opening under mild conditions, applicable in batch and continuous flow processes. These methods utilize

A palladium‐catalyzed double consecutive C(alkenyl)–H activation/alkyne insertion method utilizing a free carboxylic acid as a directing group in the preparation of functionalized naphthalenes is reported. The reaction mechanism involves a sequence of the C (alkenyl)−H activation/alkyne insertion/1,4‐palladium migration/reductive elimination steps. The second alkyne insertion occurred at the phenyl

A photocatalytic methodology has been devised for the stereoselective construction of trisubstituted alkenes incorporating 3,3‐difluoro‐γ‐lactams in 17‐93% yields via a radical cascade process utilizing MBH acetates and N‐allylbromodifluoroacetamides as starting materials. The reaction mechanism involves single‐electron transfer, 5‐exo‐trig cyclization, radical addition, and elimination in a cascade

While arylazo sulfones have been widely applied as arylating agents, their exploitation for diazenylation reactions has been previously limited to electron‐rich alkenes such as styrenes and silyl enol ethers. Herein we optimized a synthetic one‐pot protocol to access oxazolyl azo compounds via a selective domino ring‐closing/aryldiazenylation sequence by starting from arylazo sulfones and isocyanoacetamides

Biomass has been identified as the ultimate sustainable resource for all carbon‐based consumer products of the chemical industries in the future. Its catalytic conversion leads to the formation of various platform chemicals that could partially or even fully replace the fossil‐based building blocks that have been currently used in synthetic chemical processes. Among these compounds, levulinic acid

Quinoxaline is a chemical moiety known for its diverse physicochemical and biological properties, making it the focus of extensive research. Over the past few decades, quinoxaline scaffolds have been utilized in the design and development of various bioactive molecules, dyes, fluorescent materials, electroluminescent materials, organic sensitizers for solar cells, and polymeric optoelectronic materials

α‐Aryl glycines are among the more important carbonyl compounds, particularly as nonproteinogenic α‐amino acids present in many pharmacophores. As such, many strategies have been developed to access this motif, but direct carboxylation methods remain underdeveloped. Herein, we employ a dual NHC/HAT catalysis strategy to access 2‐azaallyl radicals, which subsequently couple with in situ generated ester

In this work, we extend the one‐pot protocol to synthesize 1,2‐diazepines from commercially available and cheap starting materials. Capitalizing on isocyanate derivatives as activating agents, the photochemical skeletal enlargement occurs, while preserving key functional groups embedded in more than 30 substrates. We also demonstrated that isocyanates can be generated in situ exploiting the wealth

Herein, we report a multidimensional screening strategy to discover Electron Donor‐Acceptor (EDA) complex photochemical reactions using only simple photographic devices, such as webcams or cellphones, combined with TLC analysis. An algorithm was designed to automatically identify EDA‐complex reactive mixtures in solution by processing digital images from a 96‐well microplate, alongside TLC results

An iodine‐mediated C=C double bond‐forming reaction has been established to access various fused quinolinone derivatives under transition metal‐free conditions. The present reaction is also applicable to the synthesis of fused quinolinium frameworks from the corresponding precursors and can be conducted on a gram scale.

An umpolung strategy for the C(sp3)‐H aminomethylation of 2‐methylindole has been developed using trifluoroacetic acid to induce the transformation, with aminals serving as precursors of iminium ion. Mechanistic studies have clearly shown that trifluoroacetic acid may play a pivotal role in this strategy. The utilization of readily available starting materials, mild reaction conditions, tolerance to

The C(sp3)‐H functionalization via intramolecular hydride transfer initiated cascade annulation for the synthesis of spiro‐fused succinimide‐containing tetrahydroquinolines induced by iminium intermediates is described. A series of diastereoselective 2,7‐diazaspiro[4.5]decanes‐1,3‐diones were achieved using ortho‐amino‐benzylidene‐succinimide using Lewis acid catalysis. This scandium triflate Sc(OTf)3

Deuterated hydroxyl acids and amino acids have been widely utilized in life science, biochemistry and drug development. Site‐selective and stereoselective synthesis of deuterated hydroxyl acids and amino acids remains a significant challenge. Here, we report the development of a robust whole‐cell‐based chemoenzymatic platform for the synthesis of deuterated hydroxyl acids and amino acids from off‐the‐shelf

We describe a fluorinative ring‐cleavage reaction that breaks C–C bonds in cyclic β‐diketones bearing aryl moiety using N‐fluorobenzenesulfonimide (NFSI) in the presence of inorganic carbonates (Cs2CO3 or K2CO3) in methanol at room temperature within one hour. Generated fluorinated keto acid esters bearing ortho‐nitro aryl groups were transformed into fluorinated dihydropyrido[1,2‐a]indolones (DHPIs)

A series of 4‐sulfoximinocyclopent‐2‐en‐1‐ones were prepared in 35 to 99% yield through a calcium(II)‐catalyzed aza‐Piancatelli reaction, including in enantioenriched form. Depending on their substitution pattern, diverse diastereoselective chemical transformations can be applied to these scaffolds, allowing access to cyclopentane derivatives. This study opens synthetic routes to cyclopentane‐based

The front cover presents the conversion of simple benzene derivatives into high-value trifluoromethyl-containing cyclohexadienes. The background shows the gate of Qiushi Academy, which is the former site of Zhejiang University. With a chromium-mediated η6-coordination strategy to activate inert arene π-bonds, both dearomative 1,2-hydrotrifluoromethylation and dearomative 1,2-deuterotrifluoromethylation

We describe a selective preparation of a variety of functionalized pyrrolo[2,3‐c]tetrahydroquinolines and indolo[3,2‐c]tetrahydroquinolines in 40‐82% and 40‐80% yields from alkynyl‐tethered oximes with diaryliodonium triflates, respectively. The one‐pot reaction underwent N‐arylation, intramolecular [3+2] cycloaddition, selective [1.3] or [3,3]‐rearrangement of N‐O bond in total three steps. Experimental

The insertion of diazo carbene into Si−H bonds with unsupported nanoporous copper (CuNPore) catalyst has been developed. α‐Aryl diazoesters, diazophosphonates, and unstable aryl diazoalkyls can be used as carbene precursors to exquisitely insert into the Si−H bond of silanes. A variety of α‐silylesters, silylphosphonate, and functionalized arylsilane were obtained in 35−82% yields. The reusability

An approach for the synthesis of quinoxaline‐2,3‐diamines is reported using a palladium‐catalyzed cyclization reaction of o‐phenylenediamines and isocyanides. Various quinoxaline‐2,3‐diamines could be obtained in 25%‐95% yields at 100 °C for 3 h. The key to the success of this protocol involves the formation of two C‐N and one C‐C bonds via the double insertion of isocyanide.

The ever‐increasing prevalence of diseases and inadequate resources on Earth are threats to society. Biomass is an abundant resource, and bioactive compounds produced from biomass are environmentally benign in contrast to conventional chemical synthesis methods, which frequently depend on non‐renewable resources. In addition, the functionalized monomers from biomass allow the atom economical synthesis