Palladium‐Catalyzed Oxidative Cycloisomerization of 2‐Cinnamyl‐1,3‐Dicarbonyls: Synthesis of Functionalized 2‐Benzyl Furans

A new palladium‐catalyzed intramolecular oxidative cycloisomerization of readily available starting materials, 2‐cinnamyl‐1,3‐dicarbonyls, has been demonstrated for the creation of structurally diverse 2‐benzyl furans. The cycloisomerization occurs by a regioselective 5‐exo‐trig pathway. The reaction shows a broad substrate scope with good to excellent yields. Furthermore, a one‐pot procedure has been executed by using readily available cinnamyl alcohols and 1,3‐diketones.     

Substrate‐Selective Catalysis

Substrate selectivity is an important output function for the validation of different enzyme models, catalytic cavity compounds, and reaction mechanisms as demonstrated in this review. In contrast to stereo‐, regio‐, and chemoselective catalysis, the field of substrate‐selective catalysis is under‐researched and has to date generated only a few, but important, industrial applications. This review points out the broad spectrum of different reaction types that have been investigated in substrate‐selective catalysis. The present review is the first one covering substrate‐selective catalysis and deals with reactions in which the substrates involved have the same reacting functionality and the catalysts is used in catalytic or in stoichiometric amounts. The review covers real substrate‐selective catalysis, thus only including cases in which substrate‐selective catalysis has been observed in competition between substrates.     

An Efficient Three‐component,One‐pot Synthesis of Quinazolines under Solvent‐free and Catalyst‐free Condition

An efficient green protocol for the synthesis of quinazolines in the absence of solvent and catalyst has been developed. 2,4‐Disubstituted quinazolines have been synthesized from three‐component one‐pot reactions of 2‐aminoaryl ketones, orthoesters, and ammonium acetate. The present method has advantages of operational simplicity, substrate generality, clean reaction, high yields (76–94%), and moderate reaction time. The plausible mechanism of the reaction has been proposed based on the spectral characterization and single crystal X‐ray analysis of isolated intermediate.     

Olefin‐Directed Palladium‐Catalyzed Regio‐ and Stereoselective Hydroboration of Allenes

An olefin‐directed palladium‐catalyzed regio‐ and stereoselective hydroboration of allenes has been developed to afford fully substituted alkenylboron compounds. The reaction showed a broad substrate scope: a number of functionalized allenes, including 2,3‐dienoate, 3,4‐dienoate, 3,4‐dienol, 1,2‐allenylphosphonate, and alkyl‐substituted allenes, could be used in this olefin‐directed allene hydroboration. The olefin unit was proven to be an indispensable element for this transformation.     

Stereocontrolled Organocatalytic Strategy for the Synthesis of Optically Active 2,3‐Disubstituted cis‐2,3‐Dihydrobenzofurans

An intramolecular, organocatalyzed Michael addition has been developed to obtain biologically important 2,3‐disubstituted cis‐2,3‐dihydrobenzofurans. By using mandelic acid salts of primary aminocatalysts, derived from cinchona alkaloids, the intramolecular cyclization reaction has been developed to proceed in high yield, with moderate to good diastereoselectivity, and up to 99 % ee. Based on the absolute configuration of the formed 2,3‐disubstituted‐cis‐2,3‐dihydrobenzofurans and by considering the observed substrate scope restrictions, a mechanistic rationalization has been presented.     

Electrochemical Functional‐Group‐Tolerant Shono‐type Oxidation of Cyclic Carbamates Enabled by Aminoxyl Mediators

An electrochemical method has been developed for α‐oxygenations of cyclic carbamates by using a bicyclic aminoxyl as a mediator and water as the nucleophile. The mediated electrochemical process enables substrate oxygenation to proceed at a potential that is approximately 1 V lower than the redox potential of the carbamate substrate. This feature allows for functional‐group compatibility that is inaccessible with conventional Shono oxidations, which proceed by direct electrochemical substrate oxidation. This reaction also represents the first α‐functionalization of non‐activated cyclic carbamates with oxoammonium oxidants.     

Site‐Selective O‐Arylation of Glycosides

Direct and site‐selective O‐arylation of carbohydrates has been a challenge in synthesis. Herein we report a method based on copper‐catalyzed O‐arylation to address this challenge. Proper choice of the ancillary ligand on copper is critical for the efficiency and site selectivity of this transformation. This method features mild conditions, tolerates various functional groups, and demonstrates broad substrate scope.     

Nickel‐Catalyzed Heck‐Type Monofluoroacetation of Styrenes for Facile Synthesis of Allylic Fluorides

An efficient nickel‐catalyzed Heck‐type reaction between styrenes and fluoroalkyl iodine has been developed. This novel transformation has demonstrated a broad substrate scope, mild reaction conditions and excellent E‐stereoselectivity. This efficient synthetic method has been applied to the late‐stage monofluoroacetation of biologically active molecules. Mechanistic investigations indicate that a monofluoroalkyl radical is involved in the catalytic cycle.     

Highly Selective Construction of Seven‐Membered Carbocycles by Olefin‐Assisted Palladium‐Catalyzed Oxidative Carbocyclization–Alkoxycarbonylation of Bisallenes

An olefin‐assisted palladium‐catalyzed oxidative carbocyclization–alkoxycarbonylation of bisallenes to afford seven‐membered carbocycles has been established. This dehydrogenative coupling reaction showed excellent substrate scope and functional group compatibility. The reaction exhibited high chemo‐ and regioselectivity, and ester 3 was the only product obtained. The olefin unit has been proven to be indispensable during the reaction. Moreover, intramolecular oxidative coupling suggests that the reaction proceeds via a (π‐allyl)palladium intermediate.     

A Straightforward One‐Pot Synthesis of 3,4‐Dihydroquinazoline‐2(1H)‐thione Derivatives in Aqueous Organic Solvent

A novel and efficient method has been developed for the synthesis of a series of 3,4‐dihydroquinazoline‐2(1H)‐thione derivatives in aqueous organic solvent starting from 3‐(2‐aminophenyl)acrylates with isothiocyanates via a tandem intermolecular nucleophilic addition/intramolecular Michael addition reaction under mild conditions. A broad substrate scope has been demonstrated, which shows wide functional group tolerance and chemical specialization. The efficiency of the methodology could make this process available on gram‐scale.     

An Efficient One‐pot Three‐component Method for the Synthesis of 5‐Amino‐3‐(2‐oxo‐2H‐chromen‐3‐yl)‐7‐aryl‐7H‐thiazolo[3,2‐a]pyridine‐6,8‐dicarbonitriles

A facile, convenient, and adequate method has been developed for the synthesis of novel 5‐amino‐3‐(2‐oxo‐2H‐chromen‐3‐yl)‐7‐aryl‐7H‐thiazolo[3,2‐a]pyridine‐6,8‐dicarbonitriles ( 6 ) by employing 2‐(4‐(2‐oxo‐2H‐chromen‐3‐yl)thiazol‐2‐yl)acetonitrile ( 3 ) as an important precursor. Initially, we have synthesized the target compounds in a stepwise manner and then approached a tandem method to examine the feasibility of one‐pot method. Subsequently, one‐pot three‐component protocol has been established for the synthesis of title compounds by the reaction of 3 with benzaldehyde and malononitrile in refluxing ethanol engender a new six‐membered thiazolo[3,2‐a] pyridine as a hybrid scaffold. Reaction conditions were optimized for this reaction and a broad substrate scope with various aryl and heteroaryl aldehydes make this protocol very practical, attractive, and worthy. Mechanistic aspects for the formation of these compounds were outlined comprehensively. Characterization of these newly synthesized compounds was achieved by means of IR, ¹H NMR, ¹³C NMR, and HRMS.     

Magnetic digital microfluidics on a bioinspired surface for point‐of‐care diagnostics of infectious disease

Magnetic digital microfluidics uses magnetic force to manipulate droplets on a Teflon‐coated substrate through the added magnetic particles. To achieve a wide range of droplet manipulation, hydrophilic patterns, known as surface energy traps, are introduced onto the Teflon‐coated hydrophobic substrate. However, the Teflon‐coated substrate is difficult to modify because it is nonwettable, and existing techniques for patterning surface energy traps have many limitations. Inspired by the mussel adhesion mechanism, we use polydopamine, a bioinspired substance that adheres strongly to almost any materials, to pattern surface energy traps on the Teflon‐coated substrate with a great ease. We have optimized the polydopamine coating protocol and characterized the surface properties of the polydopamine surface energy traps. Droplet operations including particle extraction, liquid dispensing, liquid shaping, and cross‐platform transfer have been demonstrated on the polydopamine surface energy trap‐enabled magnetic digital microfluidic platform in both single‐plate and two‐plate configurations. Furthermore, the detection of hepatitis B surface antigen using ELISA has been demonstrated on the new magnetic dgitial microfluidic platform. This new bioinspired magnetic digital microfluidic platform is easy to fabricate and operate, showing a great potential for point‐of‐care applications.     

Grain‐Boundary‐Free Super‐Proton Conduction of a Solution‐Processed Prussian‐Blue Nanoparticle Film

A porous crystal family has been explored as alternatives of Nafion films exhibiting super‐proton conductivities of ≥10⁻² S cm⁻¹. Here, the proton‐conduction natures of a solution‐processed film of nanoparticles (NPs) have been studied and compared to those of a Nafion film. A mono‐particle film of Prussian‐blue NPs is spontaneously formed on a self‐assembled monolayer substrate by a one‐step solution process. A low‐temperature heating process of the densely packed, pinhole‐free mono‐particle NP film enables a maximum 10⁵‐fold enhancement of proton conductivity, reaching ca. 10⁻¹ S cm⁻¹. The apparent highest conductivity, compared to previously reported data of the porous crystal family, remains constant against humidity changes by an improved water‐retention ability of the film. In our proposed mechanism, the high‐performing solution‐processed NP film suggests that heating leads to the self‐restoration of hydrogen‐bonding networks throughout their innumerable grain boundaries.     

Gold‐Catalyzed 6‐Exo‐Dig Cycloisomerization: A Versatile Approach to Functionalized Phenanthrenes

A novel gold‐catalyzed 6‐exo‐dig cycloisomerization of o‐propargylbiaryls has been developed that provides ready access to functionalized phenanthrenes in largely good to excellent yields. Notable features of this method are readily available starting materials, mild reaction conditions, and broad substrate scope.     

Catalytic Enantioselective α‐Fluorination of 2‐Acyl Imidazoles via Iridium Complexes

The first highly enantioselective α‐fluorination of 2‐acyl imidazoles utilizing iridium catalysis has been accomplished. This transformation features mild conditions and a remarkably broad substrate scope, providing an efficient and highly enantioselective approach to obtain a wide range of fluorine‐containing 2‐acyl imidazoles which are found in a variety of bioactive compounds and prodrugs. A large scale synthesis has also been tested to demonstrate the potential utility of this fluorination method.     

Rhodium(III)‐Catalyzed Directed C−H Amidation of N‐Nitrosoanilines and Subsequent Formation of 1,2‐Disubstituted Benzimidazoles

An efficient rhodium‐catalyzed direct C−H amidation of N ‐nitrosoanilines with 1,4,2‐dioxazol‐5‐ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2‐disubstituted benzimidazoles via an HCl‐mediated deprotection/cyclization process in one pot.     

Visible‐light‐driven self‐cleaning SERS substrate of silver nanoparticles and graphene oxide decorated nitrogen‐doped titania nanotube array

Graphene oxide (GO) and silver nanoparticles (Ag NPs) sequentially decorated nitrogen‐doped titania nanotube array (N‐TiO₂ NTA) had been designed as visible‐light‐driven self‐cleaning surface‐enhanced Raman scattering (SERS) substrate for a recyclable SERS detection application. N‐TiO₂ NTA was fabricated by anodic oxidation and then doping nitrogen treatment in ammonia atmosphere, acting as a visible‐light‐driven photocatalyst and supporting substrate. Ag/GO/N‐TiO₂ NTA was prepared by decorating GO monolayer through an impregnation process and then depositing Ag NPs through a polyol process on the surface of N‐TiO₂ NTA, acting as the collection of organic molecule and Raman enhancement. The SERS activity of Ag/GO/N‐TiO₂ NTA was evaluated using methyl blue as an organic probe molecule, revealing the analytical enhancement factor of 4.54 × 10⁴. Ag/GO/N‐TiO₂ NTA was applied as active SERS substrate to determine a low‐affinity organic pollutant of bisphenol A, revealing the detection limit of as low as 5 × 10^?7 m . Ag/GO/N‐TiO₂ NTA could also achieve self‐cleaning function for a recycling utilization through visible‐light‐driven photocatalytic degradation of the adsorbed organic molecules. Ag/GO/N‐TiO₂ NTA has been successfully reused for five times without an obvious decay in accuracy and sensitivity for organic molecule detection. The unique properties of this SERS substrate enable it to have a promising application for the sensitive and recyclable SERS detection of low‐affinity organic molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

Gold‐Catalyzed Cycloisomerization of Yne‐Vinylidenecyclopropanes: A Three‐Carbon Synthon for [3+2] Cycloadditions

A novel type of yne‐vinylidenecyclopropanes (VDCPs) has been synthesized and applied in gold‐catalyzed cycloisomerization reactions. It was found that these compounds can undergo an intramolecular cycloisomerization and perform as a three‐carbon synthon for [3+2] cycloaddition under gold catalysis to give fused [4.3.0] and [5.3.0] bicyclic derivatives and VDCP rearranged products in moderated to good yields under mild conditions. The substrate scope of these novel transformations has been explored and plausible reaction mechanisms have been presented on the basis of deuterium labeling experiments and DFT calculations.     

Ligand‐Promoted meta‐C−H Functionalization of Benzylamines

Meta‐C−H functionalization of benzylamines has been developed using a Pd^II/transient mediator strategy. Using 2‐pyridone ligands and 2‐carbomethoxynorbornene (NBE‐CO₂Me) as the mediator, arylation, amination, and chlorination of benzylamines are realized. This protocol features a broad substrate scope and is compatible with heterocylic coupling partners. Moreover, the loading of the Pd can be lowered to 2.5 mol % by using the optimal ligand.     

Synthesis of Substituted 2‐Amino‐1,3‐oxazoles via Copper‐Catalyzed Oxidative Cyclization of Enamines and N,N‐Dialkyl Formamides

A facile synthesis of 2‐amino‐1,3‐oxazoles via Cu^I‐catalyzed oxidative cyclization of enamines and N ,N ‐dialkyl formamides has been developed. The reaction proceeds through an oxidative C−N bond formation, followed by an intramolecular C(sp²)−H bond functionalization/C−O cyclization in one pot. This protocol provides direct access to useful 2‐amino‐1,3‐oxazoles and features protecting‐group‐free nitrogen sources, readily available starting materials, a broad substrate scope and mild reaction conditions.