Photoredox-catalyzed C(sp3)─H radical functionalization to enable asymmetric synthesis of α-chiral alkyl phosphine.

α-Chiral alkyl phosphines are privileged structural motifs with a wide application in organic and medical synthesis. It is highly desirable to develop stereoselective methods to prepare these enantioenriched molecules. The incorporation of C(sp3)─H functionalization and chiral phosphine chemistry is much less explored, probably because of the weak reactivity of C(sp3)─H bonds and/or the challenging site- and stereoselectivity issues. Herein, we disclose a synergistic catalysis system to enable an enantioselective radical addition process of α-substituted vinylphosphine oxides. An array of diverse α-chiral alkyl phosphors compounds is smoothly accessed by using the readily available chemicals as the inert C(sp3)─H bond reagent, such as sulfides, amines, alkenes, and toluene derivatives, exerting remarkable chemo-, site-, and enantioselectivity. On the basis of the mechanistic studies, both the C(sp3)─H bond activation and the stereochemistry-determining step are proposed to involve a single-electron transfer/proton transfer process.

Asymmetric Three-Component Radical Alkene Carboazidation by Direct Activation of Aliphatic C-H Bonds.

Azide compounds are widely present in natural products and drug molecules, and their easy-to-transform characteristics make them widely used in the field of organic synthesis. The merging of transition-metal catalysis with radical chemistry offers a versatile platform for radical carboazidation of alkenes, allowing the rapid assembly of highly functionalized organic azides. However, the direct use of readily available hydrocarbon feedstocks as sp3-hybridized carbon radical precursors to participate in catalytic enantioselective carboazidation of alkenes remains a significant challenge that has yet to be addressed. Herein, we describe an iron-catalyzed asymmetric three-component radical carboazidation of electron-deficient alkenes by direct activation of aliphatic C-H bonds. This approach involves intermolecular hydrogen atom transfer between a hydrocarbon and an alkoxy/aryl carboxyl radical, leading to the formation of a carbon-centered radical. The resulting radical then reacts with electron-deficient alkenes to generate a new radical species that undergoes chiral iron-complex-mediated C-N3 bond coupling. An array of valuable chiral azides bearing a quaternary stereocenter were directly accessed from widely available chemical feedstocks, and their synthetic potential is further demonstrated through more facile transformations to give other valuable enantioenriched building blocks.

Effect of a novel dwarfing mutant site on chromosome 4B on agronomic traits in common wheat.

The introduction of dwarfing genes triggered a wave of "green revolution". A number of wheats dwarfing genes have been reported in previous studies, and only a small fraction of these have been applied to production practices. Therefore, the development of novel dwarfing genes for wheat is of great value. In this study, a novel dwarfing site, Rht-yz, identified in the Yanzhan mutation, is located on chromosome 4B (30-33MB) and its mechanism of action is different from that of Rht-B1b (C-T mutation), but whether it affects the Rht-B1a (TraesCS4B02G043100) or other genes is unclear. Exogenously applied GA3 experiments showed that Rht-yz is one of the gibberellin-insensitive dwarf genes. The effects of the dwarf gene Rht-yz on agronomic traits in wheat were evaluated in the field using Yanzhan, Yanzhan mutations, F2:3 and F3:4 lines. The results showed that Rht-yz improved lodging resistance by reducing plant height, increasing diameter, wall thickness and mechanical strength of the basal stem. In terms of yield traits, Rht-yz had negative effects on tiller number plant-1, biomass plant-1 and yield plant-1, but had no significant effect on harvest index, 1000-kernel weight and spike traits. In addition, Rht-yz significantly increased crude protein, wet gluten and starch content. Therefore, the rational use of the new dwarfing site Rht-yz has potential and value in dwarf wheat breeding.

Cu-Catalyzed Enantioselective Protoboration of 2,3-Disubstituted 1,3-Dienes.

A Cu-catalyzed regio- and enantioselective protoboration of 2,3-disubstituted 1,3-dienes is described. The protocol operates under mild conditions and is applicable to symmetrically and unsymmetrically substituted dienes, providing access to homoallylic boronates in consistently high yield, regioselectivity, and enantiomeric ratio. Preliminary investigations point to a complex mechanism.

Metal-organic frameworks/metal nanoparticles as smart nanosensing interfaces for electrochemical sensors applications: a mini-review.

Metal-organic frameworks (MOFs) are porous materials with huge specific surface area and abundant active sites, which are composed of metal ions or clusters and organic ligands in the form of coordination bonds. In recent years, MOFs have been successfully applied in many fields due to their excellent physical, chemical, and biological properties. Electrochemical sensors have advantages such as economy, portability, and sensitivity, making them increasingly valued in the field of sensors. Many studies have shown that the electrode materials will affect the performance of electrochemical sensors. Therefore, the research on electrode materials is still one of the hotspots. MOFs are also commonly used to construct electrochemical sensors. However, electrochemical sensors prepared from single MOFs have shortcomings such as insufficient conductivity, low sensitivity, and poor electrochemical catalytic ability. In order to compensate for these defects, a new type of nanocomposite material with very ideal conductivity was formed by adding metal nanoparticles (MNPs) to MOFs. The combination of the two is expected to be widely applied in the field of sensors. This review summarizes the applications of various MNPs/MOFs composites in the field of electrochemical sensors and provides some references for the development of MNPs/MOFs composites-based electrochemical sensors in the future.

Photoredox-catalyzed diastereoselective dearomative prenylation and reverse-prenylation of electron-deficient indole derivatives.

Prenylated and reverse-prenylated indolines are privileged scaffolds in numerous naturally occurring indole alkaloids with a broad spectrum of important biological properties. Development of straightforward and stereoselective methods to enable the synthesis of structurally diverse prenylated and reverse-prenylated indoline derivatives is highly desirable and challenging. In this context, the most direct approaches to achieve this goal generally rely on transition-metal-catalyzed dearomative allylic alkylation of electron-rich indoles. However, the electron-deficient indoles are much less explored, probably due to their diminished nucleophilicity. Herein, a photoredox-catalyzed tandem Giese radical addition/Ireland-Claisen rearrangement is disclosed. Diastereoselective dearomative prenylation and reverse-prenylation of electron-deficient indoles proceed smoothly under mild conditions. An array of tertiary α-silylamines as radical precursors is readily incorporated in 2,3-disubstituted indolines with high functional compatibility and excellent diastereoselectivity (>20:1 d.r.). The corresponding transformations of the secondary α-silylamines provide the biologically important lactam-fused indolines in one-pot synthesis. Subsequently, a plausible photoredox pathway is proposed based on control experiments. The preliminary bioactivity study reveals a potential anticancer property of these structurally appealing indolines.

Efficient visible-light-driven S-scheme AgVO3/Ag2S heterojunction photocatalyst for boosting degradation of organic pollutants.

The traditional semiconductor photocatalysts for solving the related environmental aggravation are often challenged by the recombination of photogenerated carriers. Designing an S-scheme heterojunction photocatalyst is one of the keys to tackling its practical application problems. This paper reports an S-scheme AgVO3/Ag2S heterojunction photocatalyst constructed via a straightforward hydrothermal approach that exhibits outstanding photocatalytic degradation performances to the organic dye Rhodamine B (RhB) and antibiotic Tetracycline hydrochloride (TC-HCl) driven by visible light. The results show that AgVO3/Ag2S heterojunction with a molar ratio of 6:1 (V6S) possesses the highest photocatalytic performances, 99% of RhB can be almost degraded by 0.1 g/L V6S within 25 min light illumination, and about 72% of TC-HCl can be photodegraded with the act of 0.3 g/L V6S under 120 min light irradiation. Meanwhile, the AgVO3/Ag2S system exhibits superior stability and maintains high photocatalytic activity after 5 repeated tests. Moreover, the EPR measurement and radical capture test identify that superoxide radicals and hydroxyl radicals mainly contribute to the photodegradation process. The present work demonstrates that constructing an S-scheme heterojunction can effectively inhibit the recombination of carriers, providing insights into the fabrication of applied photocatalysts for practical wastewater purification treatment.

Recent advances in metal-catalysed asymmetric sigmatropic rearrangements.

Asymmetric sigmatropic rearrangement is a powerful organic transformation via substrate-reorganization to efficiently increase molecular complexity from readily accessible starting materials. In particular, a high level of diastereo- and enantioselectivity can be readily accessed through well-defined and predictable transition states in [3,3], [2,3]-sigmatropic rearrangements, which have been widely applied in the synthesis of various chiral building blocks, natural products, and pharmaceuticals. In recent years, catalytic asymmetric sigmatropic rearrangements involving chiral metal complexes to induce stereocontrol have been intensively studied. This review presents an overview of metal-catalysed enantioselective versions of sigmatropic rearrangements in the past two decades, mainly focusing on [3,3], [2,3], and [1,3]-rearrangements, to show the development of substrate design, new catalyst exploitation, and novel cascade processes. In addition, their application in the asymmetric synthesis of complex natural products is also exemplified.

Achieving Giant Piezoelectricity and High Property Uniformity Simultaneously in a Relaxor Ferroelectric Crystal through Rare-Earth Element Doping.

The low uniformity in properties of relaxor ferroelectric crystals is a long-standing issue in the ferroelectric community, which limits the available volume of the entire crystal boule. The aim of this study is to develop a relaxor ferroelectric crystal with improved property uniformity and excellent piezoelectricity. To this end, Pb(In1/2 Nb1/2 )O3 -Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 is doped with Nd2 O3 (Nd-PIN-PMN-PT) to improve the crystal performance. Along the crystal boule, the piezoelectric coefficient d33 varies from 2800 to 3500 pC N-1 , and the dielectric constant ranges from 8400 to 9800, with variations of 25% and 16%, respectively. Such high property uniformity results in over 75% available volume of the crystal boule, compared to 30-50% for undoped crystals grown by Bridgman method. At the electric field of 1 kV cm-1 , the converse piezoelectric response is up to 4780 pm V-1 . In addition, its Curie temperature (TC ) and coercive field (EC ) are above 150 °C and 3 kV cm-1 , respectively. Compared with Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 crystal (d33 : 1500 pC N-1 , TC : 135 °C, EC : 2.3 kV cm-1 ), the larger piezoelectricity, the higher TC and EC , and improved uniformity make Nd-PIN-PMN-PT crystals promising candidates for advanced piezoelectric applications.

Diastereo- and Enantioselective Construction of Vicinal All-Carbon Quaternary Stereocenters via Iridium/Europium Bimetallic Catalysis.

The diastereo- and enantioselective construction of vicinal all-carbon quaternary stereocenters is a formidable task. We here report a synergistic bimetallic catalysis via a chiral N,N'-dioxide-europium (Eu) complex and a phosphoramidite-iridium (Ir) catalyst for the asymmetric allylation of oxindole derivatives by using challenging trisubstituted allylic esters. The allylated products bearing vicinal all-carbon quaternary stereocenters were obtained with good diastereoselectivities (up to 20 : 1 dr) and excellent enantioselectivities (up to 99 % ee). Control experiments showed that the complementary diastereomers of the products were not accessible by the change of the stereochemistry of the chiral N,N'-dioxide ligand.

Enantioselective construction of cis-hydroindole scaffolds via an asymmetric inverse-electron-demand Diels-Alder reaction: application to the formal total synthesis of (+)-minovincine.

cis-Hydroindole scaffolds widely exist in a large number of natural products, pharmaceuticals, and organocatalysts. Therefore, the development of efficient and enantioselective methods for the construction of cis-hydroindoles is of great interest and importance. Herein, a novel approach for the enantioselective synthesis of cis-hydroindole scaffolds has been realized through a chiral N,N'-dioxide/Mg(OTf)2 complex catalyzed asymmetric inverse-electron-demand Diels-Alder (IEDDA) reaction of 2-pyrones and cyclic enamines. A series of substituted cis-hydroindole derivatives bearing multiple contiguous stereocenters and functional groups were obtained in good to excellent yields and enantioselectivities (up to 99% yield, and 95% ee) under mild reaction conditions. Moreover, the enantioselective formal total synthesis of (+)-minovincine was concisely furnished with high efficiency and stereoselectivity to demonstrate the synthetic potential of this method.

Photoinduced Chemo-, Site- and Stereoselective α-C(sp3 )-H Functionalization of Sulfides.

The ubiquity of sulfur-containing molecules in biologically active natural products and pharmaceuticals has long attracted synthetic chemists to develop efficient strategies towards their synthesis. The strategy of direct α-C(sp3 )-H modification of sulfides provides a streamlining access to complex sulfur-containing molecules. Herein, we report a photoinduced chemo-, site- and stereoselective α-C(sp3 )-H functionalization of sulfides using isatins as the photoredox reagent and coupling partner catalyzed by a chiral gallium(III)-N,N'-dioxide complex. The reaction proceeds through a verified single-electron transfer (SET) mechanism with high efficiency, excellent functional group tolerance, as well as a broad substrate scope. Importantly, this cross-coupling protocol is highly selective for the direct late-stage functionalization of methionine-related peptides, regardless of the inherent structural similarity and complexity of diverse residues.

Bimetallic Palladium/Cobalt Catalysis for Enantioselective Allylic C-H Alkylation via a Transient Chiral Nucleophile Strategy.

An asymmetric allylic C-H functionalization has been developed by making use of transient chiral nucleophiles, as well as bimetallic synergistic catalysis with an achiral Pd0 catalyst and a chiral N,N'-dioxide-CoII complex. A variety of ß-ketoesters and N-Boc oxindoles coupled with allylbenzenes and aliphatic terminal alkenes were well tolerated, furnishing the desired allylic alkylation products in high yields (up to 99 %) with excellent regioselectivities and enantioselectivities (up to 99 % ee).

Frequency Dependence of Coercive Fields of [001]- and [011]-Poled Rhombohedral Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 Single Crystals.

Relaxor-PbTiO3 (PT-based) ferroelectric single crystals are important for many piezoelectric applications because of their outstanding performances. In order to expand their usage and avoid the failure during application, frequency dependence of coercive fields EC for [001]- and [011]-poled rhombohedral Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) single crystals was investigated from the frequency of 1 Hz to 300 kHz by using hysteresis loop measurement (frequency: from 1 Hz to 2 kHz) and a critical value method (frequency: from 5 to 300 kHz). The results showed that the coercive field EC , remnant polarization Pr , and saturation polarization Ps strongly depended on the crystal orientation and frequency. Compared with the [001]-poled crystals, the [011]-poled PIN-PMN-PT single crystals possessed higher EC , Pr , and Ps at the same testing frequencies. With increasing frequency from 1 Hz to 300 kHz, the coercive fields EC of the [001]- and [011]-poled PIN-PMN-PT single crystals increased from 4.0 and 4.8 kV/cm to 11.5 and 14.9 kV/cm, respectively. Moreover, the frequency dependence of the coercive fields was found to be consistent with the growth kinetics model, where the coercive fields EC were proportional to fß . This work benefits to the design of piezoelectric devices based on PIN-PMN-PT single crystals operated at high frequencies and high driving fields.

A Catalytic Dual Isomerization/Allylboration Sequence for the Stereoselective Construction of Congested Secondary Homoallylic Alcohols.

A catalytic sequence for the diastereo- and enantioselective preparation of homoallylic alcohols with an adjacent quaternary (stereo)center is reported. The one-pot process relies on the use of a single (achiral or chiral) iridium complex to catalyze the concomitant isomerization of primary allylic alcohols and homoallylboronates into (chiral) aldehydes and allylboronates, respectively. In the same flask, a chiral Brønsted acid is added next to engage the isomerization products into a stereocontrolled allylboration reaction. Structural variations have been performed on both the allylic alcohols and the homoallylboronates. This mild process affords an array of stereochemically congested and complex chiral secondary homoallylic alcohols in high yield, excellent diastereoselectivity, and usually high enantioselectivity.

Direct Access to Chiral Secondary Amides by Copper-Catalyzed Borylative Carboxamidation of Vinylarenes with Isocyanates.

A Cu-catalyzed borylative carboxamidation reaction has been developed using vinylarenes and isocyanates. Alkynes, branched 1,3-dienes, and bicyclic alkenes were also found to be competent coupling partners. Using a chiral phosphanamine ligand, an enantioselective variant of this transformation was developed, affording a set of α-chiral amides with unprecedented levels of enantioselectivity. The synthetic utility of the method was demonstrated through a series of representative stereoretentive postcatalytic derivatizations.

Temperature Dependence of Elastic, Piezoelectric, and Dielectric Matrixes of [001]-Poled Rhombohedral PIN-PMN-PT Single Crystals.

To date, the complete sets of electromechanical-related coefficients of Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (PIN-PMN-PT) single crystals have been reported only at room temperature (RT). To meet the demands of practical applications, the full sets of elastic, piezoelectric, and dielectric constants of [001]-poled rhombohedral PIN-PMN-PT single crystals were measured as a function of temperature ranging from -10 °C to 70 °C by the resonance method. Variation trends of the material constants with temperature are discussed, and the corresponding mechanisms are analyzed. With increasing temperature, absolute values of the elastic compliance constants, the piezoelectric coefficients dij , and the dielectric permittivities εij increase, but the piezoelectric voltage coefficients gij and the characteristic frequencies decrease. The electromechanical coupling factors kij are not sensitive to temperature, of which k33 keeps 91% in the temperature range of -10 °C to 70 °C. Compared with other coefficients, the piezoelectric coefficients d31 , d33 , and d15 , and the dielectric permittivities ε11T , ε33T , ε11S , and ε33S , show the largest enhancements with increasing temperature. For example, the piezoelectric coefficients d31 and d33 , and the dielectric permittivities ε11T and ε33T change from -560 pC/N, 1130 pC/N, 1050, and 3300 at -10 °C to -890 pC/N, 1700 pC/N, 2030, and 6140 at 70 °C, increasing by more than 50% from -10 °C to 70 °C.

Copper-catalyzed enantioselective 1,2-borylation of 1,3-dienes.

A highly enantioselective Cu-catalyzed borylation of 2-substituted 1,3-dienes is reported. The use of a chiral phosphanamine ligand is essential in achieving high chemo-, regio-, diastereo- and enantioselectivity. It provides access to a variety of homoallylic boronates in consistently high yield and enantiomeric excess with 2-aryl and 2-heteroaryl 1,3-dienes as well as sterically demanding 2-alkyl 1,3-dienes. Preliminary investigations based on a non-linear effect study point to a mechanism involving more than one metal center.

Dock2 in the development of inflammation and cancer.

An atypical guanine exchange factor, Dock2 is specifically expressed in hematopoietic cells and regulates activation and migration of immune cells through activating Ras-related C3 botulinum toxin substrate (Rac). Dock2 was shown to be critical in the development of various inflammatory diseases, including allergic diseases, HIV infection, and graft rejection in organ transplantation. DOCK2 mutation in infants was recently identified to be associated with T and B cell combined immunodeficiency. Furthermore, Dock2 is involved in host protection during enteric bacterial infection and is also associated with the proliferation of cancer cells. It was also shown that patients with digestive tract cancer had high frequency mutation of DOCK2. This review summarizes the latest research progresses on the role of Dock2 for the development of various inflammatory diseases and cancers, and discusses the potential application of Dock2 modulators for patient treatment.

Biomimetic Total Synthesis of (±)-Homodimericin†A.

A biomimetic total synthesis of racemic homodimericin A was achieved in seven steps, including two cascade reactions. Aqueous buffer solutions are found to help both the oxidative dimerization cascade and the intramolecular Diels-Alder cascade. This synthetic sequence validates key steps in the biogenetic proposal of homodimericin A.