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Various substituted indolizidinium, quinolizinium and pyrido[1,2-a]azepinium salts synthesized from benzaldehydes (or α,β-unsaturated aldehydes) and alkyne-amines catalyzed by rhodium complexes via C-H activation are demonstrated. The reaction was carried out under mild reaction conditions using Cu(BF4)2·6H2O as oxidant and anion source and inexpensive oxygen as a co-oxidant. A reaction mechanism involving imine formation followed by an ortho C-H activation, alkyne insertion and reductive elimination via a 7-membered rhodacycle is proposed. The present method has been successfully applied to the synthesis of a natural product, ficuseptine.

A highly chemo- and stereoselective nickel-catalyzed borylative cyclization of 1,6-enynes with bis(pinacolato)diboron is described. Enynes containing an electron-deficient alkene such as a vinyl ketone provided alkenylboronates while enynes containing a terminal alkene gave homoallylic boronates. A plausible mechanism involving a nickelacyclopentene intermediate is proposed. In addition, the resulted alkenyl- or homoallylic boronates can be transformed to the corresponding ketones and alcohols via oxidation. Application to a palladium-catalyzed cross coupling reaction of alkenylboronates with aromatic halides has been demonstrated as well.

Thermally activated delayed fluorescence (TADF) emitters are attractive for display and lighting applications. Here, a series of highly efficient blue TADF emitters including 3,5-bis((3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)(pyridin-4-yl)methanone (4BPy-mDTC), (3,5-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)(pyridin-3-yl)methanone (3BPy-mDTC), (3,5-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)(pyridin-2-yl)methanone (2BPy-mDTC) and (3,5-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)(phenyl)methanone (BP-mDTC) were designed and synthesized. The molecular structures feature two meta carbazole substituents attached to a benzoylpyridine (BPy) group or to a benzophenone (BP) group. These compounds show high thermal stability (Td = 371–439 °C), blue emissions (458–488 nm), high photoluminescence quantum yields (PLQY) (75–96%) in thin films and very small energy gaps between S1 and T1 (ΔEST) of 0.01–0.05 eV. In addition, they all reveal TADF properties including small ΔEST, two components in the transient PL decays, prompt emission and temperature-dependent delayed emission. The BPy series appears to give much higher photoluminescence quantum yields (PLQY > 92%) than BP-mDTC (75%) plausibly due to the more rigid structure caused by the interaction between pyridine nitrogen and the aromatic C–H bond. Furthermore, 4BPy-mDTC shows a more delayed component compared to 3BPy-mDTC and 2BPy-mDTC. The electroluminescent devices based on 4BPy-mDTC and 2BPy-mDTC as the dopant emitters exhibit sky blue emission with maximum external quantum efficiencies (EQEs) over 28%, and current and power efficiency and maximum luminance up to 67.0 cd A−1, 60.1 lm W−1 and 20 000 cd m−2, respectively. The presence of the pyridine ring and the position of the nitrogen atom in the molecules are critical for the high quantum yield and device efficiency. The PLQY EQE and luminance are dramatically improved by changing the phenyl into a pyridine group in the dopant in these devices.

Three new quinoline TADF emitters, 2QPM-mDC, 2QPM-mDTC, and 4QPM-mDTC, were designed and synthesized and the emitters show ΔEST as low as 0.07 eV and high PL quantum yield (PLQY) up to 98%. An electroluminescence device based on 2QPM-mDTC can reach high EQE over 24%. Compared with the reported TADF devices, the device shows narrow emission bandwidth and high color purity. The excellent device performance is likely ascribed to the molecular design of 2QPM-mDTC containing an intramolecular H-bonding in the molecule.

Catalytic C-H functionalization has emerged as an efficient alternative to traditional coupling reactions. However, some of these reactions depend on environmentally harmful solvents, weakening the overall green nature of these methods. As organic processes consume large amount of solvents, the use of less harmful solvents enhance the sustainability of these reactions. Herein, we present an overview of transition metal-catalyzed C-H functionalization reactions for the synthesis of heterocycles in sustainable solvents based on CHEM21 solvent selection guide.

After the revelation of nonvisual lighting impact on human health, the lighting engineers are more concerned about the human benign light with low cost and high efficiency. The solution-processed fabrication technique with smart device engineering for high efficacy OLED devices is being anticipated to drastically reduce the fabrication cost leading to affordable desired end product. The co-host matrix could be a potential solution to improve device performance multi-folds with suitable band-gap engineering and most effective energy transfer from mixed host to guest. Here, rationally configured device architecture with two novel host materials possessing wide energy gap, high triplet energy, and excellent thermal and morphological stability resulted in highly-efficient solution-processed green, red and low color temperature (CT) OLEDs with sub-bandgap level driving voltage of 2.1 V i.e. record lowest within its own category. Perfect triplet energy match of our newly developed host materials with commercial p-type host m-MTDATA and the common phosphors enabled efficient energy transfer with very low energy loss led to high efficiency of resulting OLED. The resultant solution-processed triplet emitter based green and red OLED devices displayed a maximum efficacy of 75.0 and 30.2 lm W−1 without using light extraction out-coupling techniques, respectively. The designed blue-hazard free 2048 K low CT OLED exhibited a ηPE of 44.5 lmW−1, a ηCE of 47.6 cdA-1 and an EQE of 20.7% as the maximum value, the highest known so far within its own category. The melatonin suppression sensitivity (MSS) of the engineered low CT OLED is only 1.0% to that of the 480 nm blue light, which is much safer compared to other light sources. The impact of our design engineering was established by fabricating 1 cm × 1 cm device area prototype.

A cobalt-catalyzed oxidative annulation of amides with allenes to provide isoquinolin-1(2 H)-ones and pyridones was explored. The new catalytic reaction proceeded through aminoquinoline-directed C−H activation followed by unusual regioselective insertion, annulation, and isomerization. A variety of functionalized amides and allenes were converted into the corresponding products under mild reaction conditions.

Palladium-catalyzed cycloaromatization of N-acyl-2-aminobiaryls, through a sequence of ortho C−H bond activation/alkyne insertion/meta C−H bond activation/alkyne insertion, was developed. An efficient synthesis of multiaryl-substituted naphthalenes, N-[2-(5,6,7,8-tetraarylnaphthalen-1-yl)aryl]acetamides, was demonstrated using molecular oxygen as the sole oxidant. Furthermore, through Buchwald's synthetic protocol, two compounds were converted into corresponding fluorescent carbazoles in 30–40% yield by intramolecular C−N bond formation.

A highly regioselective synthesis of pyrido[2,1-a]isoindolium salts from 2-arylpyridines and two equivalents of electron-deficient alkenes catalyzed by rhodium is demonstrated. The reaction was carried out in aqueous medium at 110 °C using inexpensive oxygen as oxidant. Reverse aza-Michael addition of the isoindolium salt occurs when the salt was treated with base to give a β-disubstituted alkene product. A reaction mechanism involving an ortho C–H olefination of 2-arylpyridine by alkene, intramolecular aza-Michael addition, deprotonation at the β-carbon of the alkene fragment followed by another Michael addition to give the final product is proposed.

We have successfully synthesized a series of blue thermally activated delayed fluorescence emitters, BPy-pC, BPy-pTC, BPy-p2C, and BPy-p3C, bearing a 4-benzoylpyridine core as the electron-accepting unit and carbazolyl, tert-butylcarbazolyl, dicarbazolyl, and tercarbazolyl groups as the electron-donating units, respectively. The density functional theory calculation shows that all of the compounds have their lowest unoccupied molecular orbitals on the benzoylpyridine moiety. However, the highest occupied molecular orbital (HOMO) of BPy-p3C is widely dispersed to the whole tercarbazolyl group, while the HOMOs of BPy-pC and BPy-pTC are mainly on the carbazolyl and extended to the phenyl ring. As a result, ΔEST is reduced from 0.29 eV for BPy-pC to 0.05 eV for BPy-p3C, and the organic light-emitting diodes using these materials as dopants emit blue light and their maximum external quantum efficiencies (EQEs) increase from 4.2% to 23.9% for BPy-pC and BPy-p3C, respectively. The EQE of the BPy-p3C-based device...

An efficient C-H activation method for the ortho alkynylation of aromatic N-methoxyamides with hypervalent iodine-alkyne reagent using a ruthenium catalyst is described. The reaction proceeds under mild reaction conditions with broad substrate scope. A possible catalytic cycle involving a ruthenium carboxylate assisted C-H bond cleavage is proposed from the preliminary mechanistic evidence.

An iron-catalyzed synthesis of α,β-unsaturated carboxylic acids from alkynes and carbon dioxide was developed. This reaction proceeds through hydromagnesiation of alkynes followed by carbon dioxide insertion under atmospheric pressure and ambient temperature in the presence of iron and a Grignard reagent as a catalyst and hydride source, respectively. Several symmetrical and unsymmetrical alkynes were transformed into the corresponding acids in good to excellent yields. The methodology provides an efficient route to the synthesis of vinyl carboxylic acids.

A new cobalt-catalyzed phenolic OH-assisted C–H functionalization of 2-vinylphenols with allenes to give various 2H-chromenes is described. It is the first time that allenes are used as the coupling partners in the cobalt-catalyzed C–H activation reactions. In most cases, cobalt-catalyzed oxidative annulation of arenes with alkenes or alkynes via C–H activation gave [4 + 2] or [3 + 2] cyclization products, but the present catalytic reaction afforded an oxidative [5 + 1] cyclization products with the allenes acting as a one-carbon coupling partner. The catalytic reaction is proposed to proceed via the C–H activation of the vinyl group, allene insertion, and an unusual intramolecular regioselective phenoxide addition.

A concise approach to the synthesis of oxindoles and phenanthridones from anilides is described. In the presence of catalytic amount of Pd(OAc) 2 , 2-iodoacetates and 2-iodobenzoates can be used to functionalize ortho C–H bond of anilides, which subsequently undergo intramolecular cyclization to give the products. A possible reaction mechanism that involves a Pd II /Pd IV catalytic cycle is proposed with the support of detailed mechanistic studies.

A highly diastereoselective method for the synthesis of dihydroepoxybenzofluorenone derivatives from aromatic/vinylic amides and bicyclic alkenes is described. This new transformation proceeds through cobalt-catalyzed C-H activation and intramolecular nucleophilic addition to the amide functional group. Transition-metal-catalyzed C-H activation reactions of secondary amides with alkenes usually lead to [4+2] or [4+1] annulation; to the best of our knowledge, this is the first time that a [3+2] cycloaddition is described in this context. The reaction proceeds under mild conditions and tolerates a wide range of functional groups. Mechanistic studies imply that the C-H bond cleavage may be the rate-limiting step.

Two benzoylpyridine-carbazole based fluorescence materials DCBPy and DTCBPy, bearing two carbazolyl and 4-(t-butyl)carbazolyl groups, respectively, at the meta and ortho carbons of the benzoyl ring, were synthesized. These molecules show very small ΔEST of 0.03 and 0.04 eV and transient PL characteristics indicating that they are thermally activated delayed fluorescence (TADF) materials. In addition, they show extremely different photoluminescent quantum yields in solution and in the solid state: in cyclohexane the value are 14 and 36%, but in the thin films, the value increase to 88.0 and 91.4%, respectively. The OLEDs using DCBPy and DTCBPy as dopants emit blue and green light with EQEs of 24.0 and 27.2%, respectively, and with low efficiency roll-off at practical brightness level. The crystal structure of DTCBPy reveals a substantial interaction between the ortho donor (carbazolyl) and acceptor (4-pyridylcarbonyl) unit. This interaction between donor and acceptor substituents likely play a key role to achieve very small ΔEST with high photoluminescence quantum yield.

A novel copper-promoted multiple aza-[4 + 2] cycloaddition reaction of N-methyleneanilines in situ generated from benzylic azide and alkenes afforded quinolinium salts, biquinolinium salts, biquinolines or substituted quinolines depending on the substitution on the phenyl ring of benzylic azide. The reaction of para substituted benzylic azides and 2 equivalents of alkenes afforded the corresponding substituted quinolinium salts, while benzylic azides without a para substituent provided biquinolinium salts. The copper-promoted cycloaddition reaction also allows biquinoline products to be obtained from ortho-substituted benzylic azides. These reactions work well with both terminal and internal alkenes. Unsymmetrical internal alkene reactions proceed with high regioselectivity. The reaction is likely started by Lewis acidic CuII-assisted rearrangement of benzylic azide to N-methyleneaniline, followed by a [4 + 2] cycloaddition with alkene. Detailed mechanistic studies suggest that the biquinoline and biquinolinium salts are likely formed via radical processes.

A novel p-type charge generation material, DPAF, composed of a ferrocene core and a bis(biphenyl)amino group is designed and synthesized for application to tandem OLED devices. This molecular design not only enhances the thermal properties of ferrocene and the hole mobility, but also maintains its electrochemical stability. The red, green, and blue tandem OLEDs all give excellent device performance with low efficiency roll-off by using n-type C60 and p-type DPAFs as charge generation layers.

Correction for ‘Superior upconversion fluorescence dopants for highly efficient deep-blue electroluminescent devices’ by Yi-Hsiang Chen et al., Chem. Sci., 2016, DOI: 10.1039/c6sc00100a.

A thermally activated delayed fluorescent (TADF) material containing two meta carbazolyl groups on the phenyl ring of the benzoyl-4-pyridine moiety was prepared and its luminescence showed a colour change from blue to green by external stimuli. The organic-blue-light-emitting device using this TADF dopant provided a high external quantum efficiency of 18.4%.

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (M

We describe a highly step and atom economical cobalt-catalyzed cyclization of 1,6-enynes with aldehydes to synthesize functionalized pyrrolidines and dihydrofurans with high chemo- and stereoselectivity. The catalytic reaction plausibly proceeds via the cobaltacycle intermediate generated from the reaction of enyne substrate with cobalt catalyst, followed by switchable C-H functionalization of weakly coordinating aldehydes depending on the electronic nature of the ligand.

The host materials designed for highly efficient white phosphorescent organic light-emitting diodes (PhOLEDs) with power efficiency (PE) >50 lm W-1 and low efficiency roll-off are very rare. In this work, three new indolocarbazole-based materials (ICDP, 4ICPPy, and 4ICDPy) are presented composed of 6,7-dimethylindolo[3,2-a]carbazole and phenyl or 4-pyridyl group for hosting blue, green, and red phosphors. Among this three host materials, 4ICDPy-based devices reveal the best electroluminescent performance with maximum external quantum efficiencies (EQEs) of 22.1%, 27.0%, and 25.3% for blue (FIrpic), green (fac-Ir(ppy)3), and red ((piq)2Ir(acac)) PhOLEDs. A two-color and single-emitting-layer white organic light-emitting diode hosted by 4ICDPy with FIrpic and Ir(pq)3 as dopants achieves high EQE of 20.3% and PE of 50.9 lm W−1 with good color stability; this performance is among the best for a single-emitting-layer white PhOLEDs. All 4ICDPy-based devices show low efficiency roll-off probably due to the excellent balanced carrier transport arisen from the bipolar character of 4ICDPy.

Recent progress in frustrated Lewis pairs (FLPs) has attracted increasing attention. However, most of the FLPs are composed of Lewis basic phosphines and Lewis acidic boranes. In 2015, Kinjo and co-workers reported the first intramolecular boron-boron FLP, namely, 1,3,2,5-diazadiborinine (1), which showed high regioselectivity in the reactions with methyl trifluoromethansulfonate, phenylacetylene, and CO2. More interestingly, the activation of CO2 was found to be reversible when the temperature was elevated to 90 °C. Here, we performed thorough density functional theory (DFT) calculations to understand the stability, reactivity, and selectivity of 1. The electronic effects and favorable orbital overlap of 1 with substrates play a crucial role in the reactivity and regioselectivity. On the basis of the results, several organic substrates activated by 1, including aldehyde, ketone, imine, hydrogen, ammonia, phosphine, and silane, were explored computationally. The results show that the combination of aldehyde, ketone, imine, and silane are reversible, especially at elevated temperatures. Finally, we modeled the hydrophosphination of Me2PH and phenylacetylene catalyzed by 1. The rate-determining step is the hydrophosphination with an activation barrier of 31.7 kcal/mol, indicating that the process might be possible. Our results may open an avenue to design new organocatalysts.

A method for the synthesis of substituted quinolizinium salts from 2-ethylpyridines and alkynes is demonstrated. The transformation is conveniently achieved using 1 mol % of a Rh(III) catalyst along with an excess amount of copper(II) salt. The reaction gives high product yields with broad substrate scope and functional group tolerance. Detailed mechanistic studies suggest that 2-vinylpyridine is formed in situ from 2-ethylpyridine by a copper-promoted C(sp3)–H hydroxylation, followed by dehydration. Later, a Rh(III)-catalyzed pyridine-directed vinylic C(sp2)–H activation and annulation with alkynes provided the final product.

A highly regio- and stereoselective synthesis of 3,3-disubstituted phthalides from aryl carboxylic acids and allenes using a rhodium(III) catalyst has been demonstrated. The reaction features broad functional group tolerance and provides a simple and straightforward route to the synthesis of various 3-vinyl-substituted phthalides. Furthermore, the catalytic reaction can also be applied to the synthesis of biologically active 5-vinyl-substituted 2-furanones from α,β-unsaturated carboxylic acids and allenes. The reactions proceed through a carboxylate-assisted ortho-CH activation and [4+1] annulation. The preliminary mechanistic studies suggest that a CH cleavage is the rate-determining step.

Over the last three decades, transition-metal-catalyzed organic transformations have been shown to be extremely important in organic synthesis. However, most of the successful reactions are associated with noble metals, which are generally toxic, expensive, and less abundant. Therefore, we have focused on catalysis using the abundant first-row transition metals, specifically cobalt. In this Account, we demonstrate the potential of cobalt catalysis in organic synthesis as revealed by our research. We have developed many useful catalytic systems using cobalt complexes. Overall, they can be classified into several broad types of reactions, specifically [2 + 2 + 2] and [2 + 2] cycloadditions; enyne reductive coupling; reductive [3 + 2] cycloaddition of alkynes/allenes with enones; reductive coupling of alkyl iodides with alkenes; addition of organoboronic acids to alkynes, alkenes, or aldehydes; carbocyclization of o-iodoaryl ketones/aldehydes with alkynes/electron-deficient alkenes; coupling of thiols with aryl and alkyl halides; enyne coupling; and C-H bond activation. Reactions relying on π components, specifically cycloaddition, reductive coupling, and enyne coupling, mostly afford products with excellent stereo- and regioselectivity and superior atom economy. We believe that these cobalt-catalyzed π-component coupling reactions proceed through five-membered cobaltacyclic intermediates formed by the oxidative cyclometalation of two coordinated π bonds of the substrates to the low-valent cobalt species. The high regio- and stereoselectivity of these reactions are achieved as a result of the electronic and steric effects of the π components. Mostly, electron-withdrawing groups and bulkier groups attached to the π bonds prefer to be placed near the cobalt center of the cobaltacycle. Most of these transformations proceed through low-valent cobalt complexes, which are conveniently generated in situ from air-stable Co(II) salts by Zn- or Mn-mediated reduction. Overall, we have shown these reactions to be excellent substitutes for less desirable noble-metal systems. Recent successes in cobalt-catalyzed C-H activation have especially advanced the applicability of cobalt in this field. In addition to the more common low-valent-cobalt-catalyzed C-H activation reactions, an in situ-formed cobalt(III) five-membered complex with a 1,6-enyne effectively couples with aromatic ketones and esters through ortho C-H activation, opening a new window in this research area. Interestingly, this reaction proceeds under milder reaction conditions with broad substrate scope. Furthermore, many of the reactions we have developed are highly enantioselective, including enantioselective reductive coupling of enones and alkynes, addition of organoboronic acids to aldehydes, and the cyclization of 2-iodobenzoates with aldehydes. Overall, this Account demonstrates the versatility and utility of cobalt catalysis in organic synthesis.

The Heck reaction is a well-established transition-metal catalyzed reaction for coupling alkenes with sp2 alkyl halides to give novel unsaturated compounds. Herein we report an analogous Heck-inspired, simple efficient coupling of sp3 alkyl halides with electron-withdrawing alkenes to form reductive coupling products where saturated esters are obtained. A range of acrylates were coupled with sp3 alkyl halides in the presence of Ni(PPh3)2Cl2 catalyst, Zn metal powder, CH3CN solvent, and water, at 80 °C to form the reductive Heck type saturated ester products in good yields. This strategy was further extended to couple oxabenzonorbornadiene with the alkyl halides resulting in ring opening to give rise to bicyclic alcohol products. The mechanism for both the reactions appears to be the usual oxidative-addition driven alkene insertion reaction where the water appears to act as the protonating agent.

An efficient o-arylation of pivalamides by aryl iodides via rhodium(III)-catalyzed C–H activation is demonstrated for the first time. Further, the biaryl products can be converted effectively into biologically active phenanthridine and phenanthridinone derivative.

Transition-metal-catalyzed C - H activation is considered to be an important tool in organic synthesis and has been accepted and widely used by chemists because it is straightforward, cost-effective, and environmentally friendly. A variety of functional groups have been used to direct metal complexes and achieve regioselective C - H activation. Most directing is achieved through the σ-bond coordination of functional groups to the metal catalyst, followed by ortho-selective C - H bond cleavage. However, recent work has demonstrated that π-coordinating functional groups can also assist in guiding metal complexes for site-selective C - H bond activation. This emerging approach significantly expands the scope of C - H activation reactions in organic synthesis. Herein, recent developments in this field are summarized.

Altering the luminescence properties of a material through external factors is an attractive feature that has the potential for various luminescence-related applications. Here, we report the synthesis and luminescence properties of two anthracene-based donor acceptor compounds, N,N-di-p-tolylanthracen-9-amine (TAA) and 10-bromo-N,N-di-p-tolylanthracen-9-amine (TAAB). In the solid state, the bromo-substituted compound TAAB shows reversible visible switching of the emission by external stimuli such as solvent, mechanical grinding and temperature. Single crystal X-ray studies, powder-XRD analysis and theoretical calculations reveal that switchable emission originated from the different stacking modes of TAAB. Furthermore, we have found that the bromo group interaction in the solid state plays a crucial role in this tunable emission. The other anthracene-based compound TAA does not show such switching of the emission by external stimuli. The observed changes in the luminescence of TAAB by external stimuli suggest potential applications in rewritable optical media, sensors, and optoelectronic devices.

A high glass transition temperature (Tg = 220 °C), high triplet energy gap (ET = 2.76 eV) and high electron mobility material bis(m-terphenyl)oxadiazole was readily synthesized. It can serve as a universal electron transporter for blue, green and red phosphorescent OLEDs with excellent efficiencies. The material shows high current density compared to other electron transport materials and exhibits reduced driving voltage for all color PhOLEDs irrespective of the energy level of the host materials, due to efficient electron injection from 2,5-di([1,1′:3′,1″-terphenyl]-5′-yl)-1,3,4-oxadiazole (TPOTP) to the host material. For the green PhOLED, maximum external quantum efficiency (EQE) over 25%, current efficiency of 97.6 cd A−1 and power efficiency of 100.6 lm W−1 were achieved. The red and blue devices using TPOTP as the electron transporter also show EQE higher than 23% with very low roll-off in efficiencies in practical brightness level.

In this study, we determined that the film morphologies, crystallinities, and optical properties of CH3NH3PbI3−xClx perovskite (PVSK) layers can be manipulated by incorporating a small amount of ethylammonium iodide (EAI) into the perovskite precursor solution. For our EAI-derived films, we observed higher absorbances at higher wavelengths and higher degrees of crystallinity, both of which were associated with the higher surface coverage of the PVSK films. The optimized power conversion efficiency (PCE) improved from 9.4 ± 0.76 to 10.2 ± 0.58% after the addition of 0.5 vol% of EAI. Devices based on EAI-containing PVSK exhibited extremely high stability, retaining approximately 80% of their PCEs (T80) under accelerated heating (65 °C) in a dark N2-filled glove box for over 360 h. In contrast, the corresponding normal device was relatively sensitive to this temperature, with a T80 value of only 45 h. The improved device performance (PCE, stability) arose as a result of the presence of EAI suppressing the crystallization of CH3NH3PbI3−xClx.

A novel copper promoted synthesis of substituted quinolines from various benzylic azides and internal alkynes has been demonstrated. The reaction features a broad substrate scope, high product yields and excellent regioselectivity. In contrast to the known two-step process of acid promoted [4 + 2] cycloaddition reaction and oxidation, the present methodology allows the synthesis of quinolines in a single step under neutral reaction conditions and can be applied to the synthesis of biologically active 6-chloro-2,3-dimethyl-4-phenylquinoline (antiparasitic agent) and 3,4-diphenylquinolin-2(1H)-one (p38αMAP kinase inhibitor). A plausible reaction mechanism involves rearrangement of benzylic azide to N-arylimine (Schmidt reaction) followed by intermolecular [4 + 2] cycloaddition with internal alkynes.

An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.

The hole-injection barrier between the anode and the hole-injection layer (HIL) is of critical importance to determine the device performance of organic light-emitting diodes (OLEDs). Here, we report on a record-high external quantum efficiency (EQE) (24.6% in green phosphorescence) of OLEDs fabricated on both rigid and flexible substrates, with the performance enhanced by the use of nearly defect-free and high-mobility boron-doped graphene as an effective anode and hexaazatriphenylene hexacarbonitrile as a new type of HIL. This new structure outperforms the existing graphene-based OLEDs, in which MoO3, AuCl3, or bis(trifluoromethanesulfonyl)amide are typically used as a doping source for the p-type graphene. The improvement of the OLED performance is attributed mainly to the appreciable increase of the hole conductivity in the nearly defect-free boron-doped monolayer graphene, along with the high work function achieved by the use of a newly developed hydrocarbon precursor containing boron in the graphene...

A versatile palladium-catalyzed synthesis of highly substituted α,β-unsaturated carbonyl compounds has been developed. In contrast to the known Heck-type coupling reaction of unsaturated carbonyl compounds with aryl halides, the present methodology allows the use of stable and readily available saturated carbonyl compounds as the alkene source. In addition, the reaction proceeds well with low catalyst loadings and does not require any expensive metal oxidants or ligands. A variety of saturated aldehydes, ketones, and esters are compatible for the reaction with aryl halides under the developed reaction conditions to afford α,β-unsaturated carbonyl compounds in good to excellent yields. A possible reaction mechanism involves a palladium-catalyzed dehydrogenation followed by Heck-type cross couplings.

An efficient and atom-economical method for the synthesis of substituted indenamines from N-tosylarylimines and alkynes via ruthenium(II)-catalyzed CH bond activation and annulation is described. The catalytic reaction proceeds well with a broad substrate scope and in good yields. A possible mechanism is proposed that involves imine nitrogen chelation-assisted ortho-CH bond activation of the substrate, alkyne insertion, and intramolecular insertion of the CN Ts group into the CRu bond. Isotope-labeling experiments are performed to understand the underlying mechanism of the reaction.

A new method for the synthesis of highly substituted naphthyridine-based polyheteroaromatic compounds in high yields proceeds through rhodium(III)-catalyzed multiple C-H bond cleavage and C-C and C-N bond formation in a one-pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π-conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation-assisted ortho C-H activation, alkyne insertion, and reductive elimination, is proposed for this transformation.

Low color-temperature (CT) light sources are preferred for physiologically-friendly illumination at night due to their low suppression of melatonin secretion. We fabricated low-CT hybrid organic light-emitting diodes (OLEDs) by constructing a double emissive-layer (EML) structure, with a blue-red fluorescent-phosphorescent hybrid EML and a green phosphorescent EML, separated by a bipolar inter-layer. By doping a red phosphor in a blue fluorescent mixed-host with a decent concentration, blue and red emissions from the host and dopant, respectively, were obtained. The CT of the optimized device was tuned to less than 2500 K, with the brightness ranging from 100 to 10,000 cd m(-2). In addition, the low-CT OLED exhibited much higher efficacy than other low-CT light sources, such as incandescent bulbs and candles. The maximum power efficiency and external quantum efficiency of the hybrid OLED reached 54.6 lm W-1 and 24.3%, respectively, which only rolled off to 44.2 lm W-1 and 23.6% at 1000 cd m(-2), with a CT of 1910 K. Low-CT OLEDs with high efficacy provide a promising alternative for night lighting that will safeguard human health.

A regioselective synthesis of indoles from arylhydrazine hydrochlorides with alkynes and diethyl ketone catalyzed by a rhodium complex is described. A possible mechanism involving an in-situ generated oxidizing directing group NNCR1R2 assisted ortho-CH activation and reductive elimination are proposed. The catalytic reaction is highly compatible with a wide range of functional arylhydrazines and alkynes. The reaction proceeds under mild reaction conditions and is atom-step economical.

A nickel-catalyzed regio- and stereoselective reductive coupling of oxa- and azabicyclic alkenes with activated alkenes and electron-rich alkynes is described. Thus, 7-oxabenzonorbornadienes underwent reductive coupling with various vinyl ketones such as ethyl, methyl, propyl and alpha-methyl-substituted vinyl ketones, in the presence of a nickel(II) iodide (NiI2), zinc (Zn), and water catalyst system in acetonitrile at 50 degrees C for 14 h to afford 2-alkylnaphthalenes in good to excellent yields. Under similar reaction conditions, 7-azabenzonorbornadiene derivatives provided cis-2-alkyl-1,2-dihydro-naphthalene derivatives in high yields. On the other hand, the nickel(II) iodide, tris(4-fluorophenyl)phoshine [P(4-FC6H4)(3)] and zinc catalyst system successfully catalyzed the reductive coupling reaction of electron-rich alkynes, with 7-aza- and 7-oxabenzonorbornadienes to give cis-2-alkenyl-1,2-dihydronaphthalene derivatives in good to excellent yields. In the reaction, a mild reducing agent (zinc) and simple hydrogen source (water) were used.

Moreover, the intramolecular reductive coupling of ene-phthalimide (XI) proceeds highly diastereoselective.

A practical and environmentally benign method for the synthesis of substituted quinolines via an FeCl3-catalysed coupling reaction of aldehydes, amines, and styrenes in the presence of oxygen is described. The remarkable features of this quinoline synthesis include simple operation, mild reaction conditions, a wide substrate scope, a non-toxic and inexpensive FeCl3 catalyst, readily available starting materials, the use of oxygen as an oxidant, and no hazardous byproducts.

A new strategy for the synthesis of highly substituted benzofurans from meta-substituted hydroxybenzenes and alkynes via a rhodium(III)-catalyzed activation of a sterically hindered C-H bond is demonstrated. A possible mechanism involving dual directing group assisted ortho C-H bond activation is proposed.

An efficient method for the synthesis of functionalized vinyl arenes from the reaction of N-methoxybenzamides or N-phenoxyacetamides with vinylstannanes via rhodium(iii)-catalyzed C–H activation is described. The application of the methodology for the synthesis of a natural product thalactamine and a 7-membered ring oxepine are also demonstrated.