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Acyclic carbene–ruthenium catalysts were developed for the ethenolysis. Remarkable catalytic efficiency (turnover numbers of 100 000) and excellent α-olefin selectivity (up to 98%) were exhibited.

Azobenzene-bearing photoswitchable ruthenium catalysts were developed for olefin metathesis reactions. These catalysts exhibited an on–off switching ability in ring-closing metathesis depending on ...

The photoredox-catalyzed α-aminoalkylcarboxylation of aryl allenes with CO2 and N,N-dimethylanilines is reported for the first time (26 examples, up to 96% yield). In the case of electron-deficient allenes, good regioselectivity was observed (up to 94:6), exclusively generating kinetic products over thermodynamic products. This protocol is a novel synthetic method for highly functionalized β,γ-unsaturated γ-aminobutyric esters.

Metal-free photoredox-catalyzed carbocarboxylation of various styrenes with carbon dioxide (CO2) and amines to obtain γ-aminobutyric ester derivatives has been developed (up to 91% yield, 36 examples). The radical anion of (2,3,4,6)-3-benzyl-2,4,5,6-tetra(9H-carbazol-9-yl)benzonitrile (4CzBnBN) possessing a high reduction potential (-1.72 V vs. saturated calomel electrode (SCE)) easily reduces both electron-donating and electron-withdrawing group-substituted styrenes.

Amine-containing polyelectrolytes such as polyethyleneimine (PEI) are commonly used as cathode interfacial materials (CIMs); however, they are rarely found in non-fullerene acceptor (NFA) organic solar cells due to undesirable chemical reactions between PEI and NFAs. Unveiling the nature of these chemical interactions and developing chemically stable amine-containing polyelectrolytes is inevitable for achieving highly efficient and stable NFA organic solar cells. Herein, the reaction between PEI and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN)-based NFAs was investigated using a model system. 15N-isotope labeling experiments and 2D nuclear magnetic resonance (NMR) studies revealed that the products were generated by the Michael addition reaction and existed as the keto–enol tautomers. Based on the identified undesirable reaction, we developed a series of functionalized PEIs that are compatible with INCN-based NFAs by protecting the reactive amine functional groups. Highly efficient and stable NFA organic solar cells were successfully fabricated by the use of functionalized PEIs with broad work function tunability and improved chemical stability, which led to NFA organic solar cells with high power conversion efficiency (PCE) values of over 15% and thermally stable device operation for more than 360 hours at 100 °C.

The modulation of conformational flexibility in antimicrobial peptides (AMPs) has been investigated as a strategy to improve their efficacy against bacterial pathogens while reducing their toxicity. Here, we synthesized a library of helicity-modulated antimicrobial peptoids by the position-specific incorporation of helix-inducing monomers. The peptoids displayed minimal variations in hydrophobicity, which permitted the specific assessment of the effect of conformational differences on antimicrobial activity and selectivity. Among the moderately helical peptoids, the most dramatic increase in selectivity was observed in peptoid 17, providing more than a 20-fold increase compared to fully helical peptoid 1. Peptoid 17 had potent broad-spectrum antimicrobial activity that included clinically isolated multi-drug-resistant pathogens. Compared to pexiganan AMP, 17 showed superior metabolic stability, which could potentially reduce the dosage needed, alleviating toxicity. Dye-uptake assays and high-resolution imaging revealed that the antimicrobial activity of 17 was, as with many AMPs, mainly due to membrane disruption. However, the high selectivity of 17 reflected its unique conformational characteristics, with differential interactions between bacterial and erythrocyte membranes. Our results suggest a way to distinguish different membrane compositions solely by helicity modulation, thereby improving the selectivity toward bacterial cells with the maintenance of potent and broad-spectrum activity.

Palladium complexes bearing abnormal imidazo[1,5-a]pyridine (aImPy)-based N-heterocyclic carbene ligands were developed for the homopolymerization of olefins and the copolymerization of olefins and...

Highly enantioselective conjugate addition reactions of arylboronic acids to 2-substituted chromones catalyzed by palladium complexes with new chiral Pyridine-Dihydroisoquinoline (PyDHIQ) ligands have been developed. These reactions provide highly enantioselective access to chromanones containing tetrasubstituted stereocenters. Various arylboronic acids and 2-substituted chromones can be used in the catalytic reaction to afford the chiral tetrasubstituted chromanones in good yields and excellent enantioselectivities (25 examples, up to 98% yields, up to 99% ee).

Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.

A series of ruthenium metathesis catalysts bearing fluorinated imidazo[1,5-a]pyridin-3-ylidene carbenes (F-ImPy) were developed for ethenolysis (cross metathesis with ethylene) of methyl oleate. X-ray crystal structure analysis shows Ru–F interaction, and this fluorine substitution appears to be pivotal to have stable ImPy-Ru precatalysts. Ligand structure was varied for high catalyst activity and cross metathesis selectivity in ethenolysis reaction. F-ImPy-Ru catalysts showed high selectivity in ethenolysis of methyl oleate and thermal robustness under an ethylene atmosphere.

Nickel(II) dichloride complexes with a pyridine-chelated imidazo[1,5-a]pyridin-3-ylidene py-ImPy ligand were developed as novel catalyst precursors for acrylate synthesis reaction from ethylene and carbon dioxide (CO2), a highly promising sustainable process in terms of carbon capture and utilization (CCU). Two types of ImPy salts were prepared as new C,N-bidentate ligand precursors, py-ImPy salts (3, 4a&ndash, 4e) having a pyridine group at C(5) on ImPy and a N-picolyl-ImPy salt (10) having a picolyl group at N atom on ImPy. Nickel(II) complexes such as py-ImPyNi(II)Cl2 (7, 8a&ndash, 8e) and N-picolyl-ImPyNi(II)Cl2 (12) were synthesized via transmetalation protocol from silver(I) complexes, py-ImPyAgCl (5, 6a&ndash, 6e) and N-picolyl-ImPyAgCl (11). X-ray diffraction analysis of nickel(II) complexes (7, 8b, 12) showed a monomeric distorted tetrahedral geometry and a six-membered chelate ring structure. py-ImPy ligands formed a more planar six-membered chelate with the nickel center than did N-picolyl-ImPy ligand. py-ImPyNi(II)Cl2 complexes (8a&ndash, 8e) with tert-butyl substituents exhibited noticeable catalytic activity in acrylate synthesis from ethylene and CO2 (up to 108% acrylate). Interestingly, the use of additional additives including monodentate phosphines increased catalytic activity up to 845% acrylate (TON 8).

The first palladium-catalyzed enantioselective conjugate addition reactions of arylboronic acids to 2-substituted chromones with chiral pyridine-dihydroisoquinoline ligands have been developed., Highly enantioselective conjugate addition reactions of arylboronic acids to 2-substituted chromones catalyzed by palladium complexes with new chiral Pyridine-Dihydroisoquinoline (PyDHIQ) ligands have been developed. These reactions provide highly enantioselective access to chromanones containing tetrasubstituted stereocenters. Various arylboronic acids and 2-substituted chromones can be used in the catalytic reaction to afford the chiral tetrasubstituted chromanones in good yields and excellent enantioselectivities (25 examples, up to 98% yields, up to 99% ee).

Solution-processable small molecule (SM) organic semiconductors for organic photovoltaics have been in the spotlight for several years. In particular, SM semiconductors have been developed in an attempt to control their film morphology, study their intermolecular interactions, and synthesize new electron donor and electron acceptor subunits. SMs have many advantages over polymers including well-defined molecular structures, monodispersity, and no batch-to-batch dependence. Although SM semiconductors can be designed by truncation from polymers, such examples have rarely been reported. Herein we designed SM semiconductors by truncating a representative polymer, Poly[4-(4,8-bis((2-hexyldecyl)oxy)benzo[1,2-b:4,5-b’]dithiophen-2-yl)-alt-benzo[c][1,2,5]thiadiazole] (PBDTBT). Based on density functional theory (DFT) calculations, 2,1,3-benzothiadiazole (BT) was chosen as an electron acceptor subunit instead of thieno[3,4-c]pyrrole-4,6-dione (TPD). The SM semiconductors were end-capped with pyridine derivatives. Thermal, optical and electrochemical properties of these materials were examined to confirm the degradation temperature, the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, and the band gaps. In particular, the benzyloxyl pyridine-capped semiconductor (SM1) exhibited power conversion efficiency (PCE) of 1.92% which is higher than those shown by the corresponding polymer PBDTBT (0.90% and 1.71%).

The development of artificial peroxidases has attracted great interest because of their applications in various fields such as the chemical industry and biosensing. In this study, 2,6-bis[(bis(2-pyridylmethyl)amino)-methyl]-4-methylphenol (H-bpmp) complexes with various transition metal ions have been investigated as artificial peroxidases. Among these metal complexes, the [Mn2(bpmp)]3+ complex showed the highest peroxidase-like activity as determined by a colorimetric assay using 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and H2O2. The peroxidase-like activity was inhibited by pyrophosphate (PPi), which blocked the active site of the [Mn2(bpmp)]3+ complex. Based on this phenomenon, the ABTS/H2O2/[Mn2(bpmp)]3+ system could be applied for the detection of PPi, which could be achieved selectively by visual observation with a detection limit of 130 nM. Moreover, the addition of pyrophosphatase (PPase) to the [Mn2(bpmp)]3+ complex blocked by PPi resulted in the recovery of the peroxidase-like activity of the [Mn2(bpmp)]3+ complex due to the hydrolysis of PPi. Hence, the enzyme cascade reaction of the PPase and [Mn2(bpmp)]3+ complex allowed the real-time colorimetric assay of PPase.

In this study, a colorimetric and fluorescent chemosensor for mercury ions (Hg 2+ ) was developed. Cationic polydiacetylene (PDA) vesicles with a quaternary ammonium cation and iodide as a counterion show a blue-to-red color transition; the color change is accompanied by a fluorescence enhancement in selective response to Hg 2+ ions because of a perturbation of the ene–yne conjugated backbone induced by counterion exchange. It allows for selective detection of Hg 2+ with the naked eye and the sensor is used to determine Hg 2+ concentrations in tap water samples.

Diethylene glycol-functionalized imidazo[1,5-a]pyridin-3-ylidenes (DEG-ImPy) have been developed as bifunctional N-heterocyclic carbene ligands. The DEG-ImPy Cu(I) complexes efficiently catalyzed the direct C–H carboxylation of benzoxazole with CO2, showing higher isolated yields than those with the N,N′-(2,6-diisopropylphenyl)imidazolylidene Cu catalyst.

Cation-binding salen nickel catalysts were developed for the enantioselective alkynylation of trifluoromethyl ketones in high yield (up to 99 %) and high enantioselectivity (up to 97 % ee). The reaction proceeds with substoichiometric quantities of base (10-20 mol % KOt-Bu) and open to air. In the case of trifluoromethyl vinyl ketones, excellent chemo-selectivity was observed, generating 1,2-addition products exclusively over 1,4-addition products. UV-vis analysis revealed the pendant oligo-ether group of the catalyst strongly binds to the potassium cation (K+ ) with 1:1 binding stoichiometry (Ka =6.6×105 m-1 ).

Enantioselective C(sp2)−H borylations of diarylmethylsilanes were catalyzed using iridium complexes with chiral pyridine-dihydroisoquinoline (PyDHIQ) ligands. High enantioselectivities (up to >99% ee) were observed for various substrates. A gram-scale synthesis was achieved using 1 mol% of the catalyst to afford a 91% yield of the desired chiral borylated organosilane product with >99% ee.

In this study, commercially available cellulose membranes were hybridized with conjugated polymer via vapor-phase polymerization using pyrrole and iron chloride as a monomer and oxidant, respectively. The iron (III) chloride layer dip-coated on the hydrophilic cellulose surface oxidized the vaporized pyrrole monomer leading to the polypyrrole–cellulose hybrid membrane. The conductivity of hybrid membrane was optimized by varying the oxidant concentration and the monomer vapor exposure time. The various surface characterizations of polypyrrole–cellulose hybrid membrane show that the conductive polypyrrole layer was uniformly deposited onto the surface of cellulose fibrous networks unlike the polypyrrole–nylon hybrid membrane prepared in the similar way. The polypyrrole-incorporated cellulose networks exhibits steeper electrical conductance increase over the vertical pressure than its nylon counterpart. Our result suggests that the polypyrrole–cellulose hybrid membrane can be applicable for a disposable high-load pressure sensor.

International audience; A new series of D–A–D-type small-molecule photovoltaic donors are designed and virtually screened before synthesis using time-dependent density functional theory calculations carefully validated against various polymeric and molecular donors. In this series of new design, benzodithiophene is kept as D to achieve the optimum highest-occupied molecular orbital energy level, while thienopyrroledione is initially chosen as A but later replaced by difluorinated benzodiathiazole or its selenide derivative to achieve the optimum band gap. The D–A–D core is end-capped by pyridone units which could not only enhance their self-assembly via hydrogen bonds but also play a role as an acceptor (A′) to form an extended A′–D–A–D–A′ small-molecule donor.

For several decades, the key challenge associated with thermochemical hydrogen generation has been the achievement of water splitting and catalyst regeneration at low temperatures while maintaining a reasonably high conversion efficiency over many cycles. Herein, we report low-temperature thermochemical hydrogen generation using hierarchically assembled iron oxide nanoarchitectures. Iron oxide nanoparticles conformally deposited onto a SnO2 nanowire forest allowed the splitting of water molecules and the production of hydrogen gas at temperatures of 400–800 °C, with a high specific gas-forming rate as high as ∼25000 μmol per g per cycle (250 min). More remarkably, deep-ultraviolet photoactivation enabled low-temperature (200 °C) catalyst regeneration and thereby multiple cycles of hydrogen production without any significant coalescence of the oxide nanoparticles nor substantial loss of the water-splitting efficiency. Hierarchically arranged iron oxide nanoarchitectures, in combination with photochemical catalyst regeneration, are promising for practical hydrogen generation by harvesting wasted thermal energy, even at temperatures below 500 °C.

In this research, we report a polypyrrole (PPy) multilayer-laminated cellulose network aimed at the cost-effective removal of aqueous potentially toxic metal ions with high adsorption efficiency and good adsorbent recyclability. The preparation of conformal adsorbent coatings on a fibrous cellulose network was accomplished by performing multiple cycles of simple dip-coating of a non-toxic oxidant and vapor-phase polymerization of PPy. The resultant PPy multilayer-deposited cellulose exhibited stable adhesion between the vapor-deposited PPy and the underlying cellulose support even in a strongly acidic solution. Using this non-hazardous hybrid adsorbent, mercury ions could be efficiently adsorbed over a large pH range with a maximum specific adsorption capacity of 31.689 mg g−1, either in the form of a thick suspended adsorbent for large-scale decontamination or a thin dripper-type membrane for portable water purification. Furthermore, the PPy multilayer-laminated cotton fabric enabled the large-scale repetitive removal of mercury ions (100 ppm, 1 liter) with efficiency above 91%. This study suggests that the PPy-cotton hybrid may serve as a large-scale, economical, and recyclable decontamination platform for efficient removal of highly potentially toxic metal ions (e.g., Hg(II) and Cr(VI)), which could be beneficial for water purification, particularly in resource-limited locations.

Recently, perovskite solar cells (PSCs) have emerged as an excellent photovoltaic device owing to the outstanding power conversion efficiency (PCE). Nevertheless, device instability remains a critical issue in this field. To overcome device instability without deteriorating PCE, dopant-free hole transporting materials (HTMs) are needed to separate the air-sensitive perovskite layer from extrinsic factors, which induce its degradation. Herein, we developed novel conjugate polymers of benzo[1,2- b:4,5- b']dithiophene (BDT) and 4,4-difluoro-4-bora-3 a,4 a-diaza- s-indacene (BODIPY) for use as HTMs without dopants. The pBDT-BODIPY polymer allows individual "dialing" of the highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO) levels with small modifications to the molecular structure, enabling study of the impact of the frontier molecular orbital on PSC performance. Different alkyl chains on BDT can minutely adjust the HOMO level, and meso-substituents on BODIPYs can selectively set the LUMO level of the resulting polymers. Application of BODIPY-containing polymer into the perovskite solar cell as an HTM leads to a high PCE value (16.02%) and exceptional solar cell stability shown by the fact that over 80% of its original PCE value was maintained after 10 days under ambient air conditions.

Breast cancer is classified into three groups according to its expression of hormone/growth factor receptors: (i) estrogen receptor (ER) and progesterone receptor (PR)-positive; (ii) human epidermal growth factor receptor 2 (HER2)-positive; and (iii) ER, PR, and HER2-negative (triple-negative). A series of methoxy-substituted biisoquinoline compounds have been synthesized as a potential chemotherapeutic agent for the triple-negative breast cancers which are especially challenging to manage. Structure activity relationship study revealed that rigid 6,6′-dimethoxy biisoquinoline imidazolium compound (1c, DH20931) exhibited the significant growth inhibitory effects on both triple-positive and triple-negative human breast cancer cell lines with IC50 in the range of 0.3–3.9 μM. The 1c (DH20931) is more potent than structurally related noscapine for growth inhibition of MCF7 cell line (IC50 = 1.3 vs 57 μM) and MDA-MB231 cell line (IC50 = 3.9 vs 64 μM).

The aim of this study is to enhance the recycled PVC related material property by formulation technology and develop the recycling product processing technology furthermore develop the chemical recycling technology for last stage of PVC wastes. The formulation technology is composed of pre-treatment (crushing, separation etc.) and post-treatment (material ratio, additives, stabilizer etc.) to enhance the recyclate property. The formulation for recycled PVC by application basis and processing technology is applied to produce the structural product for civil and construction application such as pipe fittings and water drainage cap for environmental waterway. Also chemical recycling technology for end life PVC scrap which causes environmental pollution by incineration or landfill is studied for producing hydrocarbon and hydrogen chloride for VCM.

A series of sterically demanding acyclic aminooxycarbenes (AAOCs) were prepared in good yields from chloroiminium salts and alkoxysilanes via the TMS-Cl elimination pathway. The steric profiles of ...

A series of isoquinoline-based chiral diimine ligands are conveniently prepared via Bischler–Napieralski cyclization. The C2-symmetric diimine ligand 1a is effective in Cu(II)-catalyzed enantioselective Henry reactions between nitromethane and various aldehydes (11 examples), showing 50–89% yield and 75–93% ee.

2-Alkylpyrrolidines were used as building blocks for acyclic diaminocarbenes (ADCs). First, ureas were made from the corresponding amines, and then the ureas were converted to chloroamidiniums. The chloroamidiniums served as direct precursors to ADCs, and palladium complexes were made utilizing oxidative addition, whereas lithium−halogen exchange was performed to generate rhodium complexes. The carbene ligands were characterized through use of NMR, mass spectrometry, and X-ray analysis, and from X-ray structures, steric parameters were calculated as % VBur values. The ability of these ligands to direct stereochemistry and enhance activity was explored in the Suzuki cross-coupling reaction and the 1,2 addition of arylboronic acids to aldehydes.

Correction for ‘Polypyrrole multilayer-laminated cellulose for large-scale repeatable mercury ion removal’ by Zahid Hanif et al., J. Mater. Chem. A, 2016, 4, 12425–12433.

A lithium-halogen exchange route has been developed to generate acyclic diaminocarbenes (ADC) from chloroamidinium salts. Convenient access to various ADC complexes (B, Rh, Ir, Pd) stems from a one-pot transmetalation protocol. Formation of a carbenoid species is suggested by 1D and 2D NMR studies with a (13)C-labeled chloroamidinium precursor and also by X-ray structures of transition metal-carbene complexes. Rh-ADC complex 4 is an effective catalyst for the 1,2-addition of aryl boronic acids to aryl aldehydes.

The design and solution-phase synthesis of an alpha-helix mimetic library as an integral component of a small-molecule library targeting protein-protein interactions are described. The iterative design, synthesis, and evaluation of the candidate alpha-helix mimetic was initiated from a precedented triaryl template and refined by screening the designs for inhibition of MDM2/p53 binding. Upon identifying a chemically and biologically satisfactory design and consistent with the screening capabilities of academic collaborators, the corresponding complete library was assembled as 400 mixtures of 20 compounds (20 x 20 x 20-mix), where the added subunits are designed to mimic all possible permutations of the naturally occurring i, i + 4, i + 7 amino acid side chains of an alpha-helix. The library (8000 compounds) was prepared using a solution-phase synthetic protocol enlisting acid/base liquid-liquid extractions for purification on a scale that insures its long-term availability for screening campaigns. Screening of the library for inhibition of MDM2/p53 binding not only identified the lead alpha-helix mimetic upon which the library was based, but also suggests that a digestion of the initial screening results that accompany the use of such a comprehensive library can provide insights into the nature of the interaction (e.g., an alpha-helix mediated protein-protein interaction) and define the key residues and their characteristics responsible for recognition.

In-rich InGaN layers were successfully grown on GaN templates by metalorganic chemical vapor deposition. In incorporation in InGaN layer was enhanced by decreasing the growth temperature, and In-rich InGaN layer with In content higher than 70% was obtained below 670 °C. Especially, double peaks from In-rich InGaN grown at 640 °C appeared in X-ray diffraction pattern and photoluminescence (PL). The further investigation of strain status of InGaN layers by reciprocal space mapping (RSM) clarified that In-rich InGaN layers were fully relaxed and consisted of InGaN alloys of two different In contents of 82% and 97%, respectively. As a result, we confirmed that compositional inhomogeneity which is mainly reported in Ga-rich InGaN layer could exist in In-rich InGaN layer higher than 80%. We also investigated In incorporation behavior in InGaN at low temperature (640 °C). In content in InGaN layer was found to be controlled by just changing input gas phase mole fraction (TMIn/(TMGa+TMIn)) at low growth temperature and a linear relationship was observed between In content in InGaN layers and gas phase mole fraction.

Families of very high-index planes, such as those which bifurcate spontaneously to form a hill-and-valley structure composed of opposing facets, provide natural templates for the directed growth of position-controlled self-organized nanostructures with shapes determined by the facet width ratio R. For example, deposition of a few ML of Ge on Si(173 100 373), corresponding to R(113/517) = 1.7, results in a field of 40-nm-wide Ge nanowires along [72 187 ] with a uniform period of 60 nm.

Organolanthanides are highly efficient catalysts for inter- and intramolecular hydroamination of various C-C unsaturations such as alkenes, alkynes, allenes, and dienes. Attractive features of organolanthanide catalysts include very high turnover frequencies and excellent stereoselectivities, rendering this methodology applicable to concise synthesis of naturally occurring alkaloids and other polycyclic azacycles. The general hydroamination mechanism involves turnover-limiting C-C multiple bond insertion into the Ln-N bond, followed by rapid protonolysis by other amine substrates. Sterically less encumbered ligand designs have been developed to improve reaction rates, and metallocene and nonmetallocene chiral lanthanide complexes have been synthesized for enantioselective hydroamination.

Organolanthanide complexes of the general type Cp'(2)LnCH(TMS)(2) (Cp' = eta(5)-Me(5)C(5); Ln = La, Sm, Y; TMS = SiMe(3)) and CGCSmN(TMS)(2) (CGC = Me(2)Si(eta(5)-Me(4)C(5))((t)()BuN)) serve as effective precatalysts for the rapid, regioselective, and highly diastereoselective intramolecular hydroamination/cyclization of primary and secondary amines tethered to conjugated dienes. The rates of aminodiene cyclizations are significantly more rapid than those of the corresponding aminoalkenes. This dienyl group rate enhancement as well as substituent group (R) effects on turnover frequencies is consistent with proposed transition state electronic demands. Kinetic and mechanistic data parallel monosubstituted aminoalkene hydroamination/cyclization, with turnover-limiting C=C insertion into the Ln-N bond to presumably form an Ln-eta(3) allyl intermediate, followed by rapid protonolysis of the resulting Ln-C linkage. The rate law is first-order in [catalyst] and zero-order in [aminodiene]. However, depending on the particular substrate and catalyst combination, deviations from zero-order kinetic behavior reflect competitive product inhibition or self-inhibition by substrate. Lanthanide ionic radius effects and ancillary ligation effects on turnover frequencies suggest a sterically more demanding Ln-N insertion step than in aminoalkene cyclohydroamination, while a substantially more negative DeltaS( double dagger ) implies a more highly organized transition state. Good to excellent diastereoselectivity is obtained in the synthesis of 2,5-trans-disubstituted pyrrolidines (80% de) and 2,6-cis-disubstituted piperidines (99% de). Formation of 2-(prop-1-enyl)piperidine using the chiral C(1)-symmetric precatalyst (S)-Me(2)Si(OHF)(CpR)SmN(TMS)(2) (OHF = eta(5)-octahydrofluorenyl; Cp = eta(5)-C(5)H(3); R = (-)-menthyl) proceeds with up to 71% ee. The highly stereoselective feature of aminodiene cyclization is demonstrated by concise syntheses of naturally occurring alkaloids, (+/-)-pinidine and (+)-coniine from simple diene precursors.

C(2)-symmetric bis(oxazolinato)lanthanide complexes of the type [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), [(4S,5R)-Ar(2)Box]La[N(TMS)(2)](2), and [(4S)-Ph-5,5-Me(2)Box]La[N(TMS)(2)](2) (Box = 2,2'-bis(2-oxazoline)methylenyl; Ar = 4-tert-butylphenyl, 1-naphthyl; TMS = SiMe(3)) serve as precatalysts for the efficient enantioselective intramolecular hydroamination/cyclization of aminoalkenes and aminodienes. These new catalyst systems are conveniently generated in situ from the known metal precursors Ln[N(TMS)(2)](3) or Ln[CH(TMS)(2)](3) (Ln = La, Nd, Sm, Y, Lu) and 1.2 equiv of commercially available or readily prepared bis(oxazoline) ligands such as (4R,5S)-Ph(2)BoxH, (4S,5R)-Ar(2)BoxH, and (4S)-Ph-5,5-Me(2)BoxH. The X-ray crystal structure of [(4S)-(t)BuBox]Lu[CH(TMS)(2)](2) provides insight into the structure of the in situ generated precatalyst species. Lanthanides having the largest ionic radii exhibit the highest turnover frequencies as well as enantioselectivities. Reaction rates maximize near 1:1 BoxH:Ln ratio (ligand acceleration); however, increasing the ratio to 2:1 BoxH:Ln decreases the reaction rate, while affording enantiomeric excesses similar to the 1:1 BoxH:Ln case. A screening study of bis(oxazoline) ligands reveals that aryl stereodirecting groups at the oxazoline ring 4 position and additional substitution (geminal dimethyl or aryl) at the 5 position are crucial for high turnover frequencies and good enantioselectivities. The optimized precatalyst, in situ generated [(4R,5S)-Ph(2)Box]La[N(TMS)(2)](2), exhibits good rates and enantioselectivities, comparable to or greater than those achieved with chiral C(1)-symmetric organolanthanocene catalysts, even for poorly responsive substrates (up to 67% ee at 23 degrees C). Kinetic studies reveal that hydroamination rates are zero order in [amine substrate] and first order in [catalyst], implicating the same general mechanism for organolanthanide-catalyzed hydroamination/cyclizations (intramolecular turnover-limiting olefin insertion followed by the rapid protonolysis of an Ln-C bond by amine substrate) and implying that the active catalytic species is monomeric.

New chiral C1-symmetric organolanthanide catalysts of the type Me2Si(OHF)(CpR*)LnN(TMS)2 (OHF = η5-octahydrofluorenyl; Cp = η5-C5H3; R* = (−)-menthyl; Ln = Sm, Y, Lu; TMS = SiMe3) have been synthesized, characterized, and implemented in the enantioselective and diastereoselective cyclizations of aminoalkenes and phosphinoalkenes. Me2Si(OHF)(CpR*)LnCl2-Li(DME)2+ catalyst precursors can be prepared in up to ∼90% diastereomeric purity and then converted into the corresponding amido catalysts, which can be isolated in ∼100% diastereomeric purity after recrystallization. The catalyst (S)-Me2Si(OHF)(CpR*)YN(TMS)2 has been crystallographically characterized. The activity of these catalysts for the hydroamination/cyclization of aminoalkenes and for the hydrophosphination/cyclization of phosphinoalkenes is described. Enantioselectivites as high as 67% are obtained in hydroamination, and diastereoselectivities of as high as 96% are obtained in hydrophosphination.

The efficient synthesis of enantioenriched compounds is becoming increasingly important in modern organic, pharmaceutical, and materials chemistry. Recently, chiral cooperative bimetallic catalysts have emerged as a powerful tool to achieve high efficiency and selectivity in asymmetric transformations. This tutorial review highlights strategies and recent advances in cooperative bimetallic catalysts which have been developed for a variety of asymmetric transformations.