Chiral Cpx Rhodium(III)-Catalyzed Enantioselective Aziridination of Unactivated Terminal Alkenes.

Chiral cyclopentadienyl-rhodium(III) Cpx Rh(III) catalysis has been demonstrated to be competent for catalyzing highly enantioselective aziridination of challenging unactivated terminal alkenes and nitrene sources. The chiral Cpx Rh(III) catalysis system exhibited outstanding catalytic performance and wide functional group tolerance, yielding synthetically important and highly valuable chiral aziridines with good to excellent yields and enantioselectivities (up to 99 % yield, 93 % ee). This protocol presents a novel and effective strategy for synthesizing enantioenriched aziridines from simple alkenes. Various transformations were performed on the aziridine products, illustrating the versatility and synthetic potential of this protocol for constructing highly functionalized compounds.

Green Preparation of a Carboxymethyl Cellulose-Coated Membrane for Highly Efficient Separation of Crude Oil-In-Water Emulsions.

Developing high-performance membranes is an extremely significant strategy to combat increasing severe oil pollution. However, most of the previously reported superwettable membranes have been inevitably involved with the use of toxic solvents and complicated preparation processes. In addition, most of them lacked the capacity of separating crude oil-in-water emulsions. Herein, a facile and green strategy is employed to fabricate a polytetrafluoroethylene (PTFE) membrane with a mixed suspension of PDA@ZIF-8 and carboxymethyl cellulose (CMC) using water as a solvent via the vacuum filtration method. Combining hydrophilic property with micro-nano-roughness, the CMC-PDA@ZIF-8-coated PTFE membrane (CPZP membrane) exhibits excellent underwater superoleophobicity. More importantly, the separation efficiency of various surfactant-stabilized oil-in-water emulsions including crude oil/water emulsion is higher than 99.2% with a flux up to 1306.5 L m-2 h-1, and the separation performance remains nearly the same after 10 cycles. Moreover, outstanding underwater superoleophobic and self-cleaning properties are maintained after long-distance sandpaper abrasion and multiple bending tests. Meanwhile, its exceptional separation performance is still maintained in harsh environments (3.5 wt % NaCl, 1 M HCl, 60 °C hot water) even after immersing it for 24 h. Therefore, this green-prepared and high-performance membrane has tremendous application prospects in treating oily wastewater.

Hierarchical Self-Assembly Pathways of Peptoid Helices and Sheets.

Peptoids (N-substituted glycines) are a class of tailorable synthetic peptidomic polymers. Amphiphilic diblock peptoids have been engineered to assemble 2D crystalline lattices with applications in catalysis and molecular separations. Assembly is induced in an organic solvent/water mixture by evaporating the organic phase, but the assembly pathways remain uncharacterized. We conduct all-atom molecular dynamics simulations of Nbrpe6Nc6 as a prototypical amphiphilic diblock peptoid comprising an NH2-capped block of six hydrophobic N-((4-bromophenyl)ethyl)glycine residues conjugated to a polar NH3(CH2)5CO tail. We identify a thermodynamically controlled assembly mechanism by which monomers assemble into disordered aggregates that self-order into 1D chiral helical rods then 2D achiral crystalline sheets. We support our computational predictions with experimental observations of 1D rods using small-angle X-ray scattering, circular dichroism, and atomic force microscopy and 2D crystalline sheets using X-ray diffraction and atomic force microscopy. This work establishes a new understanding of hierarchical peptoid assembly and principles for the design of peptoid-based nanomaterials.

Bioequivalence study of two formulations of terazosin hydrochloride capsule in healthy Chinese subjects under fasting and fed conditions.

OBJECTIVE: This study was conducted to assess the pharmacokinetic and safety profiles between a new oral formulation of terazosin hydrochloride capsule compared with the brand-name drug. MATERIALS AND METHODS: A randomized, open-label, single-dose, 2-period crossover study under fasting or fed conditions was conducted in healthy Chinese subjects. 24 individuals were selected, respectively. Each subject was randomized at the beginning to receive a 2-mg capsule of the test or the reference terazosin during the first period and then received the alternate formulation during the second period following a 1-week washout period. Blood samples were collected at pre-dose and up to 60 hours after administration. Plasma terazosin was quantified by a validated LC-MS/MS method. RESULTS: 48 healthy subjects were enrolled, and 47 completed the study. Cmax, AUC0-t, and AUC0-∞ were similar and the 90% CIs for the geometric mean ratios of these parameters between the two groups were all bounded within the predefined bioequivalence criterion of 80 - 125% under both fasting and fed conditions. Throughout the study period, a total of 30 treatment-emergent adverse events (TEAEs) were reported under fasting condition. 35 TEAEs were observed under fed conditions. No serious adverse event was observed. CONCLUSION: The test and reference formulations of terazosin were bioequivalent and well tolerated under both fasting and fed conditions.

LINC00852 promotes the proliferation and invasion of ovarian cancer cells by competitively binding with miR-140-3p to regulate AGTR1 expression.

BACKGROUND: Dysregulation of long non-coding RNAs (lncRNAs) has been identified in ovarian cancer. However, the expression and biological functions of LINC00852 in ovarian cancer are not understood. METHODS: The expressions of LINC00852, miR-140-3p and AGTR1 mRNA in ovarian cancer tissues and cells were detected by quantitative reverse transcription polymerase chain reaction (qRT-PCR) assay. Gain- and loss-of-function assays were performed to explore the biological functions of LINC00852 and miR-140-3p in the progression of ovarian cancer in vitro. The bindings between LINC00852 and miR-140-3p were confirmed by luciferase reporter gene assay, RNA immunoprecipitation (RIP) assay and RNA pull-down assay. RESULTS: We found that LINC00852 expression was significantly up-regulated in ovarian cancer tissues and cells, whereas miR-140-3p expression was significantly down-regulated in ovarian cancer tissues. Functionally, LINC00852 knockdown inhibited the viability, proliferation and invasion of ovarian cancer cells, and promoted the apoptosis of ovarian cancer cells. Further investigation showed that LINC00852 interacted with miR-140-3p, and miR-140-3p overexpression suppressed the viability, proliferation and invasion of ovarian cancer cells. In addition, miR-140-3p interacted with AGTR1 and negatively regulated its level in ovarian cancer cells. Mechanistically, we found that LINC00852 acted as a ceRNA of miR-140-3p to promote AGTR1 expression and activate MEK/ERK/STAT3 pathway. Finally, LINC00852 knockdown inhibited the growth and invasion ovarian cancer in vivo. CONCLUSION: LINC00852/miR-140-3p/AGTR1 is an important pathway to promote the proliferation and invasion of ovarian cancer.

Superhydrophobic Waste Cardboard Aerogels as Effective and Reusable Oil Absorbents.

As the main component of the municipal waste, waste cardboard has caused a host of environmental problems. Therefore, the reasonable disposal of waste cardboard is of great significance to global sustainable development and green economics. Herein, using waste cardboard as the raw material, a superhydrophobic aerogel has been developed with a unique three-dimensional porous network structure, which exhibits excellent selective oil absorption capacities. The aerogel was made by combining Ca2+ cross-links and postmodification with stearic acid. Superhydrophobic aerogels can absorb various organic solutions and its maximum absorption capacity can reach 47 times its own weight. Meanwhile, the size of aerogels has been further expanded, with a diameter of 21.2 cm and a height of 3.2 cm, which can absorb 34 times its own weight of kerosene. More importantly, the aerogel can also absorb oil droplets in oil/water emulsions with an adsorption efficiency of over 98.5%. Moreover, the aerogel can be employed multiple times without significantly reducing the adsorption capacity via distillation or squeezing, depending upon the type of pollutions. Consequently, we believe that these facile and inexpensive superhydrophobic aerogels can effectively adsorb oily wastewater, which matches well with the requirement for environmentally friendliness from the perspective of practical application.

Association of FMO3 rs1736557 polymorphism with clopidogrel response in Chinese patients with coronary artery disease.

PURPOSE: Dual antiplatelet therapy with aspirin and clopidogrel is commonly used for coronary artery disease (CAD) patients undergoing percutaneous coronary intervention to prevent stent thrombosis and ischemic events. However, some patients show high on-treatment platelet reactivity (HTPR) during clopidogrel therapy. Genetic factors such as loss-of-function variants of CYP2C19 are validated to increase the risk of HTPR. Flavin-containing monooxygenase 3 (FMO3) is reported to be associated with potency of platelet responsiveness and thrombosis. This study aimed to explore the association between FMO3 rs1736557 polymorphism and clopidogrel response. METHODS: Five hundred twenty-two Chinese CAD patients treated with dual antiplatelet therapy were recruited from Xiangya Hospital. After oral administration of 300 mg loading dose (LD) clopidogrel for 12-24 h or 75 mg daily maintenance dose (MD) clopidogrel for at least 5 days, the platelet reaction index (PRI) was determined by vasodilator-stimulated phosphoprotein-phosphorylation assay. FMO3 rs1736557, CYP2C19*2, and CYP2C19*3 polymorphisms were genotyped by polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP). RESULTS: Mean PRI value was significantly higher in CYP2C19 poor metabolizers (PMs) and intermediate metabolizers (IMs) than the extensive metabolizers (EMs) (p < 0.001). In addition, FMO3 rs1736557 AA homozygotes showed significantly lower PRI as compared with carriers of the major rs1736557 G allele in the entire cohort and in the MD cohort (p = 0.011, p = 0.008, respectively). The risk of HTPR was decreased significantly in carriers of the rs1736557 A allele (AA vs GG: OR = 0.316, 95% CI: 0.137-0.726, p = 0.005; AA vs GA: OR = 0.249, 95% CI: 0.104-0.597, p = 0.001; AA vs GG+GA: OR = 0.294, 95% CI: 0.129-0.669, p = 0.002), and the association was observed mainly in patients carrying the CYP2C19 LOF allele and in those administered with MD. CONCLUSION: The FMO3 rs1736557 AA genotype was related to an increased the antiplatelet potency of clopidogrel in Chinese CAD patients. Additional studies are required to verify this finding.

TRIM59, amplified in ovarian cancer, promotes tumorigenesis through the MKP3/ERK pathway.

Tripartite motif containing 59 (TRIM59) functions as an oncoprotein in various human cancers including ovarian cancer. In this study, we found that TRIM59 gene amplification was prevalent in ovarian cancer tissues, and its amplification was significantly correlated with poorer overall survival. Moreover, knockdown of TRIM59 in SKOV3 and OVCAR3 cells, which had relatively high level of TRIM59, suppressed glucose uptake and lactate production. TRIM59 knockdown also decreased the expression of c-Myc and lactate dehydrogenase A, and the phosphorylation of extracellular signal-regulated kinase (ERK). TRIM59 overexpression in A2780 cells, which expressed low level of TRIM59, showed reverse effects. Notably, treatment with an ERK inhibitor (PD98059) completely abolished the oncogenic effects of TRIM59 overexpression. Interestingly, TRIM59 increased the ubiquitination of MAP kinase phosphatase 3 (MKP3), which may dephosphorylate and inactivate ERK. Ectopic expression of MKP3 inhibited the promoting effects of TRIM59 on glycolysis and the phosphorylation of ERK. TRIM59 protein expression was negatively correlated with MKP3 protein expression in ovarian cancer tissues. Finally, TRIM59 amplification potently affected the anticancer effect of 3-bromopyruvate, an inhibitor of glycolysis, in ovarian cancer cells and patient-derived xenograft. In conclusion, these results suggest that TRIM59 may regulate glycolysis in ovarian cancer via the MKP3/ERK pathway.

Bioinspired Peptoid Nanotubes for Targeted Tumor Cell Imaging and Chemo-Photodynamic Therapy.

Substantial progress has been made in applying nanotubes in biomedical applications such as bioimaging and drug delivery due to their unique architecture, characterized by very large internal surface areas and high aspect ratios. However, the biomedical applications of organic nanotubes, especially for those assembled from sequence-defined molecules, are very uncommon. In this paper, the synthesis of two new peptoid nanotubes (PepTs1 and PepTs2) is reported by using sequence-defined and ligand-tagged peptoids as building blocks. These nanotubes are highly robust due to sharing a similar structure to those of nontagged ones, and offer great potential to hold guest molecules for biomedical applications. The findings indicate that peptoid nanotubes loaded with doxorubicin drugs are promising candidates for targeted tumor cell imaging and chemo-photodynamic therapy.

Solid-phase synthesis of three-armed star-shaped peptoids and their hierarchical self-assembly.

Due to the branched structure feature and unique properties, a variety of star-shaped polymers have been designed and synthesized. Despite those advances, solid-phase synthesis of star-shaped sequence-defined synthetic polymers that exhibit hierarchical self-assembly remains a significant challenge. Hence, we present an effective strategy for the solid-phase synthesis of three-armed star-shaped peptoids, in which ethylenediamine was used as the centric star pivot. Based on the sequence of monomer addition, a series of AA'A''-type and ABB'-type peptoids were synthesized and characterized by UPLC-MS (ultrahigh performance liquid chromatography-mass spectrometry). By taking advantage of the easy-synthesis and large side-chain diversity, we synthesized star-shaped peptoids with tunable functions. We further demonstrated the aqueous self-assembly of some representative peptoids into biomimetic nanomaterials with well-defined hierarchical structures, such as nanofibers and nanotubes. These results indicate that star-shaped peptoids offer the potential in self-assembly of biomimetic nanomaterials with tunable chemistries and functions.

AGXT2: An unnegligible aminotransferase in cardiovascular and urinary systems.

Cardiovascular diseases (CVDs) and renal impairment interact in a complex and interdependent manner, which makes clarification of possible pathogenesis between CVDs and renal diseases very challenging and important. There is increasing evidence showing that both asymmetric dimethylarginine (ADMA) and symmetric dimethylarginine (SDMA) play a crucial role in the development of CVDs as well as in the prediction of cardiovascular events. Also, the plasma levels of ADMA and SDMA were reported to be significantly associated with renal function. Alanine-glyoxylate aminotransferase 2 (AGXT2) is reported to be involved in ADMA and SDMA metabolism, thus deficiency in the expression or activity of AGXT2 may play a part in the progression of cardiovascular or renal diseases through affecting ADMA/SDMA levels. Here, we focused our attention on AGXT2 and discussed its potential impact on CVDs and renal diseases. Meanwhile, the review also summarized the functions and recent advances of AGXT2, as well as the clinical association studies of AGXT2 in cardiovascular and urinary systems, which might arouse the interest of researchers in these fields.

High Expression of AHSP, EPB42, GYPC and HEMGN Predicts Favorable Prognosis in FLT3-ITD-Negative Acute Myeloid Leukemia.

BACKGROUND/AIMS: Acute myeloid leukemia (AML) is a heterogeneous clonal disease and patients with AML who harbor an FMS-like tyrosine kinase 3 (FLT3) mutation present several dilemmas for the clinician. This study aims to identify novel targets for explaining the dilemmas. METHODS: We analyzed four microarray gene expression profiles to investigate changes in whole genome expression associated with FLT3-ITD mutation. RESULTS: We identified 22 differentially expressed genes which are commonly expressed among all four profiles. Kaplan-Meier analysis of the dataset GSE12417 revealed that low expression of AHSP, EPB42, GYPC and HEMGN predicted poor prognosis (AHSP: P=0.0317, HR=1.894; EPB42: P=0.0382, HR=1.859; GYPC: P=0.0015, HR=2.051; HEMGN: P=0.0418, HR=1.838 in GSE12417 test cohort; AHSP: P=0.0279, HR=1.548; EPB42: P=0.0398, HR=1.505; GYPC: P=0.0408, HR=1.501; HEMGN: P=0.0143, HR=1.630 in GSE12417 validation cohort). When patients were FLT3-ITD positive, the expression of FLT3 was significantly increased (all P<0.05 in four profiles), and correleation analysis of four profiles revealed that the expression of the four candidate genes negatively correlated with FLT3 expression. CONCLUSIONS: Our findings suggest that AHSP, EPB42, GYPC and HEMGN may be suitable biomarkers for diagnostic or therapeutic strategies for FLT3-ITD-positive AML patients.

Defect-induced enhanced photocatalytic activities of reduced α-Fe2O3 nanoblades.

Bicrystalline α-Fe2O3 nanoblades (NBs) synthesized by thermal oxidation of iron foils were reduced in vacuum, to study the effect of reduction treatment on microstructural changes and photocatalytic properties. After the vacuum reduction, most bicrystalline α-Fe2O3 NBs transform into single-layered NBs, which contain more defects such as oxygen vacancies, perfect dislocations and dense pores. By comparing the photodegradation capability of non-reduced and reduced α-Fe2O3 NBs over model dye rhodamine B (RhB) in the presence of hydrogen peroxide, we find that vacuum-reduction induced microstructural defects can significantly enhance the photocatalytic efficiency. Even after 10 cycles, the reduced α-Fe2O3 NBs still show a very high photocatalytic activity. Our results demonstrate that defect engineering is a powerful tool to enhance the photocatalytic performance of nanomaterials.

Photocatalytic Enantioselective Radical Cascade Multicomponent Minisci Reaction of ß-Carbolines Using Diazo Compounds as Radical Precursors.

Here, a photocatalytic asymmetric multicomponent cascade Minisci reaction of ß-carbolines with enamides and diazo compounds is reported, enabling an effective enantioselective radical C─H functionalization of ß-carbolines with high yields and enantioselectivity (up to 83% yield and 95% ee). This enantioselective multicomponent Minisci protocol exhibits step economy, high chemo-/enantio-selective control, and good functional group tolerance, allowing access to a variety of valuable chiral ß-carbolines. Notably, diazo compounds are suitable radical precursors in enantioselective cascade radical reactions. Moreover, the efficiency and practicality of this approach are demonstrated by the asymmetric synthesis of bioactive compounds and natural products.

Two-dimensional nanomaterial MXenes for efficient gas separation: a review.

Transition metal carbides/nitrides (MXenes) are emerging two-dimensional (2D) materials that have been widely investigated in recent years. In general, these materials can be obtained from MAX phase ceramics after intercalation, etching, and exfoliation to obtain multilayer MXene nanosheet structures; moreover, they have abundant end-group functional groups on their surface. In recent years, the excellent high permeability, fine sieving ability and diverse processability of MXene series materials make the membranes prepared using them particularly suitable for membrane-based separation processes in the field of gas separation. 2D membranes enhance the diversity of the pristine membrane transport channels by regulating the gas transport channels through in-plane pores (intrinsic defects), in-plane slit-like pores, and planar to planar interlayer channels, endowing the membrane with the ability to effectively sieve gas energy efficiently. Herein, we review MXenes, a class of 2D nanomaterials, in terms of their unique structure, synthesis method, functionalization method, and the structure-property relationship of MXene-based gas separation membranes and list examples of MXene-based membranes used in the field of gas separation. By summarizing and analyzing the basic properties of MXenes and demonstrating their unique advantages compared to other 2D nanomaterials, we lay a foundation for the discussion of MXene-based membranes with outstanding carbon dioxide (CO2) capture performance and outline and exemplify the excellent separation performances of MXene-based gas separation membranes. Finally, the challenges associated with MXenes are briefly discussed and an outlook on the promising future of MXene-based membranes is presented. It is expected that this review will provide new insights and important guidance for future research on MXene materials in the field of gas separation.

Advances in special wettable materials for adsorption separation of high-viscosity crude oil/water mixtures.

Effective separation of highly viscous crude oil/water mixtures remains a worldwide challenge. Employing special wettable materials with adsorptive properties as an emerging separation strategy has attracted extensive attention in the treatment of crude oil spillage. Such a separation technique combines excellent wettability materials and their adsorption performance to achieve energy efficient removal or recovery of high viscosity crude oil. Particularly, special wettable adsorption materials with thermal properties provide novel ideas and directions for the construction of rapid, green, economic and all-weather crude oil/water adsorption separation materials. Negatively, the high viscosity of crude oil makes most special wettable adsorption separation materials and surfaces extremely susceptible to adhesion and contamination in practical applications, leading to rapid functional failure. Moreover, such an adsorption separation strategy towards high-viscosity crude oil/water mixture separation has rarely been summarized. Consequently, there are still some potential challenges in separation selectivity and adsorption capacity of special wettable adsorption separation materials which urgently need to be summarized to guide the future development. In this review, the special wettability theories and construction principles of adsorption separation materials are first introduced. Then, the composition and classification of crude oil/water mixtures, particularly focusing on enhancing the separation selectivity and adsorption capacity of adsorption separation materials, are comprehensively and systematically discussed via regulating surface wettability, designing pore structures and reducing crude oil viscosity. Meanwhile, the separation mechanisms, construction ideas, fabrication strategies, separation performances, practical applications, and the advantages and disadvantages of special wettable adsorption separation materials are also analyzed. Finally, the challenges and future prospects for adsorption separation of high-viscosity crude oil/water mixtures are expounded.

Recent advances of slippery liquid-infused porous surfaces with anti-corrosion.

Metal materials are susceptible to the influence of environmental media, and chemical or electrochemical multiphase reactions occur on the metal surface, resulting in the corrosion of metal materials, which can directly damage the geometry and reduce the physical properties of metal materials. This corrosion damage can seriously affect the long-term use of metal materials in marine equipment and the aerospace industry, and other fields. Inspired by the special microstructure and slippery properties of natural nepenthes intine, researchers have prepared slippery liquid-infused porous surfaces (SLIPS) with a stable continuous lubricant layer by injecting low-surface-energy lubricants into a substrate with a micro/nano-porous structure. This surface has excellent hydrophobicity, low friction, non-adhesiveness, and self-healing properties. The broad application prospects of SLIPS in the fields of anti-corrosion, anti-icing, anti-bacteria, and anti-fouling have made it a hot research topic directing the study of biomimetic materials at present. However, SLIPS are susceptible to environmental shear forces, such as ocean flow or extraneous fluids, resulting in destruction of the porous structure and loss of surface lubricant, thereby depriving SLIPS of the ability to protect metals from corrosion. Therefore, it is important for metal corrosion protection to find ways to improve the stability and extend the service life of SLIPS. Over the last several years, research into and development of SLIPS have come a long way. Herein, a summary of available reports on SLIPS is given in terms of design principles and their performance characteristics, the construction of rough/porous substrate structures, the choice of low-surface-energy modifiers and lubricants, and lubricant infusion methods. Ways of constructing different substrate structures and the characteristics, advantages, and disadvantages of choosing various modifiers and lubricants to prepare the surface are compared. Finally, a comprehensive summary and outlook of SLIPS with anti-corrosion properties are provided. We are convinced that a comprehensive review of SLIPS will provide important guidance and strong reference for the design and preparation of green and economical SLIPS with anti-corrosion capabilities in the future.

Reduced graphene oxide/carbon nitride composite sponge for interfacial solar water evaporation and wastewater treatment.

Interfacial solar-driven steam generation has been proposed as a cost-effective green sustainable technology to alleviate the freshwater crisis. However, the desire to produce clean water from water sources containing organic contaminants is still remains a challenge due to the limitations of the traditional wastewater treatment methods. Here, we constructed a g-C3N4-based composite sponge solar steam generator (rGCPP) by a simple hydrothermal reaction. Benefiting from its low cost and easy preparation, this evaporator can be expected to be a promising candidate for the alleviation of water shortages and water pollution in practical applications. By combination of the solar steam generation and the photocatalysis into the rGCPP-based interfacial solar-driven steam generation system, the resulted rGCPP-based solar steam generator performs outstanding solar absorption of 90.8%, which achieves high evaporation rate of 1.875 kg m-2 h-1 and solar-to-vapor efficiency of 81.07% under 1 sun irradiation. Meanwhile, organic pollutants in the water source can be completely removed by photocatalytic degradation and the degradation rates were measured to be 99.20% for methylene blue and 91.07% for rhodamine B, respectively. Consequently, the as-prepared composite sponge has promising applications in generating clean water and alleviating water pollution.

Guanidine-Based Covalent Organic Frameworks: Cooperation between Cores and Linkers for Chromic Sensing and Efficient CO2 Conversion.

C(sp)-H carboxylation with CO2 is an attractive route of CO2 utilization and is traditionally promoted by transition metal catalysts, and organocatalysis for the conversion remains rarely explored and challenging. In this article, triaminoguanidine-derived covalent organic frameworks (COFs) were used as platforms to develop heterogeneous organocatalysts for the reaction. We demonstrated that the COFs with guanidine cores and pyrazine linkers show high catalytic performance as a result of the cooperation between cores and linkers. The core is vitally important, which is deprotonated to the guanidinato group that binds and activates CO2. The pyrazine linker collaborates with the core to activate the C(sp)-H bond through hydrogen bonding. In addition, the COFs show acid- and base-responsive chromic behaviors thanks to the amphoteric nature of the core and the auxochromic effect of the pyrazine linker. The work opens up new avenues to organocatalysts for C-H carboxylation and chromic materials for sensing and switching applications.

Photocatalytic enantioselective Minisci reaction of ß-carbolines and application to natural product synthesis.

A highly efficient enantioselective direct C-H functionalization of ß-carbolines via a Minisci-type radical process under a photo-redox and chiral phosphoric acid cooperative catalytic system has been disclosed. Through this protocol, a wide range of C1 aminoalkylated ß-carbolines were constructed directly with high levels of enantioselectivities from readily available ß-carbolines and alanine-derived redox-active esters. This transformation allows straightforward access to highly valuable enantioenriched ß-carbolines, which are an intriguing structural motif in valuable natural products and synthetic bio-active compounds. This protocol has been utilized as a highly efficient synthetic strategy for the concise asymmetric total synthesis of marine alkaloids eudistomin X, (+)-eudistomidin B and (+)-eudistomidin I.