Asymmetric α-Allylation of Amino Acid Esters with Alkynes Enabled by Chiral Aldehyde/Palladium Combined Catalysis.

A highly efficient, atom-economical α-allylation reaction of NH-unprotected amino acid esters and alkynes is achieved by chiral aldehyde/palladium combined catalysis. A diverse range of α,α-disubstituted nonproteinogenic α-amino acid esters are produced in 31-92% yields and 84-97% ee values. The allylation products are utilized for the synthesis of drug molecule BMS561392 and other chiral molecules possessing complex structures.

Asymmetric three-component Tsuji-Trost allylation reaction enabled by chiral aldehyde/palladium combined catalysis.

Despite the long-standing exploration of the catalytic asymmetric Tsuji-Trost allylation reaction since the mid-20th century, most reported instances have adhered to a two-component approach. Here, we present a remarkably efficient three-component asymmetric allylation reaction enabled by the collaborative action of chiral aldehyde and palladium. A diverse array of NH-unprotected amino acid esters, aryl or alkenyl iodides, and allyl alcohol esters exhibit robust participation in this reaction, resulting in the synthesis of structurally diverse non-proteinogenic α-amino acid esters with favorable experimental outcomes.

Bifunctional Squaramide-Catalyzed Oxidative Kinetic Resolution: Simultaneous Access to Axially Chiral Thioether and Sulfoxide.

Axially chiral thioethers and sulfoxides emerge as two pivotal classes of ligands and organocatalysts, which have remarkable features in the stereoinduction of various asymmetric transformations. However, the lack of easy methods to access such molecules with diverse structures has hampered their broader utilization. Herein, an oxidative kinetic resolution for sulfides using a chiral bifunctional squaramide as the catalyst with cumene hydroperoxide as the terminal oxidant is established.

Core Structure-Oriented Asymmetric α-Allenylic Alkylation of Amino Acid Esters Enabled by Chiral Aldehyde/Palladium Catalysis.

Aiming at the reported chiral synthons leading to manzacidins A and D, here we report a highly efficient catalytic asymmetric α-allenylic alkylation reaction of NH-unprotected amino acid esters that is promoted by combined chiral aldehyde/palladium catalysis. Fifty examples of unnatural α,α-disubstituted amino acid esters are reported with good-to-excellent yields and stereoselectivities. Based on this methodology, a key intermediate leading to manzacidin C and its other three stereoisomers is prepared accordingly.

Asymmetric α-Allylation of -Unprotected Amino Acid Esters with 1,3-Disubstituted Allyl Acetates Enabled by Chiral-Aldehyde/Palladium Catalysis.

A chiral aldehyde/palladium catalysis-enabled asymmetric α-allylation of NH-unprotected amino acid esters with 1,3-disubstituted allyl acetates is described in this work. With the utilization of different chiral phosphine ligands, both the and selective allylation reactions are achieved enantioselectively. A series of α,α-disubstituted amino acid esters bearing two adjacent chiral centers are produced in moderate-to-excellent yields, diastereoselectivities, and enantioselectivities.

Chiral aldehyde catalysis enables direct asymmetric α-substitution reaction of N-unprotected amino acids with halohydrocarbons.

The direct catalytic α-hydrocarbylation of readily available amino acids with halohydrocarbons is one of the most straightforward methods leading to α,α-disubstituted non-proteinogenic α-amino acid compounds. However, all the reported methodologies depend on N-protected amino acids as starting materials. Herein, we report on three highly efficient aldehyde-catalyzed direct α-hydrocarbylations of N-unprotected amino acid esters with aryl-, allyl-, and benzyl halides.

Chiral aldehyde-nickel dual catalysis enables asymmetric α-propargylation of amino acids and stereodivergent synthesis of NP25302.

The combined catalytic systems derived from organocatalysts and transition metals exhibit powerful activation and stereoselective-control abilities in asymmetric catalysis. This work describes a highly efficient chiral aldehyde-nickel dual catalytic system and its application for the direct asymmetric α-propargylation reaction of amino acid esters with propargylic alcohol derivatives. Various structural diversity α,α-disubstituted non-proteinogenic α-amino acid esters are produced in good-to-excellent yields and enantioselectivities.

Catalytic asymmetric Tsuji-Trost α-benzylation reaction of N-unprotected amino acids and benzyl alcohol derivatives.

Catalytic asymmetric Tsuji-Trost benzylation is a promising strategy for the preparation of chiral benzylic compounds. However, only a few such transformations with both good yields and enantioselectivities have been achieved since this reaction was first reported in 1992, and its use in current organic synthesis is restricted. In this work, we use N-unprotected amino acid esters as nucleophiles in reactions with benzyl alcohol derivatives.

Enantioselective synthesis of α-amino ketones through palladium-catalyzed asymmetric arylation of α-keto imines.

Chiral α-amino ketones are common structural motifs in natural products and pharmaceuticals, as well as important synthons in organic synthesis. Thus, establishing efficient methods for preparing compounds with these privileged scaffolds is an important endeavor in synthetic chemistry. Herein we disclose a new catalytic asymmetric approach for the synthesis of chiral α-amino ketones through a chiral palladium-catalyzed arylation reaction of generated challenging α-keto imines from previously unreported -acyl -sulfonyl-,-aminals, with arylboronic acids.

Direct Catalytic Asymmetric α-Allylic Alkylation of Aza-aryl Methylamines by Chiral-Aldehyde-Involved Ternary Catalysis System.

A ternary catalytic system comprising a chiral aldehyde, a transition metal, and a Lewis acid is rationally designed for the asymmetric α-allylic alkylation reaction of aza-aryl methylamines and π-allylmetal electrophiles. Structural diversity chiral amines bearing carbon-carbon double bonds and aza-heterocycles are produced in moderate to good yields with good to excellent enantioselectivities. These products can be readily converted into other chiral amines without the loss of enantioselectivity.

Diastereodivergent chiral aldehyde catalysis for asymmetric 1,6-conjugated addition and Mannich reactions.

Chiral aldehyde catalysis is a burgeoning strategy for the catalytic asymmetric α-functionalization of aminomethyl compounds. However, the reaction types are limited and to date include no examples of stereodivergent catalysis. In this work, we disclose two chiral aldehyde-catalysed diastereodivergent reactions: a 1,6-conjugate addition of amino acids to para-quinone methides and a bio-inspired Mannich reaction of pyridinylmethanamines and imines.

Organocatalytic Asymmetric Aldol Reaction of Arylglyoxals and Hydroxyacetone: Enantioselective Synthesis of 2,3-Dihydroxy-1,4-diones.

A highly efficient quinine-derived primary-amine-catalyzed asymmetric aldol addition of hydroxyacetone to arylglyoxals is described. Structurally diverse -2,3-dihydroxy-1,4-diones were generated in high yields, with good diastereoselectivities and enantioselectivities.

Reduced graphene oxide coated CuSe nanoparticles for targeted chemo-photothermal therapy.

Recently, copper chalcogenide semiconductors have been reported as new near-infrared (NIR) photothermal agents. However, it is difficult to modify them with recognition molecules, and their photothermal conversion efficiencies are relatively low, making it difficult to achieve the targeted photothermal ablation of cancer cells with a high efficiency. In this study, reduced graphene oxide (rGO) was first coated on the surface of CuSe nanoparticles (NPs) to provide abundant functional groups for the next modification and to increase the photothermal conversion efficiency.

Carbon dots: materials, synthesis, properties and approaches to long-wavelength and multicolor emission.

Herein, we summarize recent research developments and progress of carbon dots (CDs), which have been attracting considerable attention as a new type of photoluminescent material. Raw materials, from single carbonaceous compounds to colorful natural substances, for the synthesis of CDs are discussed. A range of diverse synthetic methodologies to achieve better photoluminescence performance and more advanced functions are summarized, and these are basically divided into two classes: top-down and bottom-up.

Selective colorimetric analysis of spermine based on the cross-linking aggregation of gold nanoparticles chain assembly.

A selective colorimetric assay for spermine was proposed in this work. In a weak alkaline medium, the conformational structure of double-stranded calf thymus DNA (ctDNA) was loosened to install gold nanoparticles (AuNPs) into chains. While, the chain assembly of AuNPs could form cross-linking aggregates when spermine was present, which was attributed to the electrostatic interaction between the positive change of spermine and negative change both of AuNPs and ctDNA, as well as the groove binding between ctDNA and spermine.

Carbon dots with aggregation induced emission enhancement for visual permittivity detection.

Photoluminescent carbon dots (CDs), hydrothermally prepared using tannic acid (TA), show visual aggregation induced emission enhancement (AIEE) properties at 455 nm when excited at 350 nm owing to the rotational hindering of the surface groups on CDs such as aromatic rings and phenolic hydroxyl ones, causing exponential decay between the ratio of the photoluminescence intensity in organic solvents to that in water and the permittivity of the solvent, and thus dazzling emissions of the CDs in the presence of solvents with small permittivity, tetrahydrofuran (THF), for instance, could be visually observed.

Germanium-doped carbon dots as a new type of fluorescent probe for visualizing the dynamic invasions of mercury(II) ions into cancer cells.

Carbon dots doped with germanium (GeCDs) were firstly prepared by a new simple 15 min carbonation synthesis route, exhibiting excitation-independent photoluminescence (PL), which could avoid autofluorescence in bioimaging applications. The as-prepared GeCDs have low cell toxicity, good biocompatibility, high intracellular delivery efficiency, stability and could be applied for detection of mercury(II) ions with excellent selectivity in complicated medium. It is to be noted that the as-prepared GeCDs used as a new type of probe for visualization of dynamic invasions of mercury(II) ions into Hep-2 cells display greatly different properties from most of the previously reported CDs which are regularly responsive to iron ions.

Reduced graphene oxide gated mesoporous silica nanoparticles as a versatile chemo-photothermal therapy system through pH controllable release.

Synergistic therapy has become a potential treatment in the battle against disease. In this work, we developed a novel versatile folate targeted system for cancer cells with the combination of chemotherapy and phototherapy by using mesoporous silica nanoparticles (MSNs) as a drug loading carrier, in which reduced graphene oxide (rGO) gated the MSNs by pH responsive detachment. That is, rGO herein acts not only for gating control of the drug release but also for near-infrared photothermal therapy.

One-pot hydrothermal synthesis of orange fluorescent silver nanoclusters as a general probe for sulfides.

Water-soluble fluorescent silver nanoclusters (AgNCs) with almost seven and nine silver atoms and a quantum yield (QY) of 5.38 ± 0.25% were successfully prepared via one-pot hydrothermal synthesis using polymethacrylic acid sodium salt (PMAA-Na) as a template.

A general quantitative pH sensor developed with dicyandiamide N-doped high quantum yield graphene quantum dots.

A general quantitative pH sensor for environmental and intracellular applications was developed by the facile hydrothermal preparation of dicyandiamide (DCD) N-doped high quantum yield (QY) graphene quantum dots (GQDs) using citric acid (CA) as the carbon source. The obtained N-doped GQDs have excellent photoluminesence (PL) properties with a relatively high QY of 36.5%, suggesting that N-doped chemistry could promote the QY of carbon nanomaterials.

A surfactant-assisted redox hydrothermal route to prepare highly photoluminescent carbon quantum dots with aggregation-induced emission enhancement properties.

Highly PL carbon quantum dots (CQDs) were successfully prepared from C60 by introducing CTAB and H2O2 in aqueous NaOH under hydrothermal conditions. The CQDs displayed a nanoparticle aggregation-induced emission enhancement (NP-AIEE).

One-pot hydrothermal synthesis of highly luminescent nitrogen-doped amphoteric carbon dots for bioimaging from Bombyx mori silk - natural proteins.

Nitrogen-doped carbon dots (CDs) have attracted great interest due to their extraordinary properties, especially their enhanced emission efficiency, and thus a facile synthesis of nitrogen-doped CDs with high emission efficiency is critical for practical applications. To improve the emission efficiency of CDs, herein we employed Bombyx mori silk, which has high nitrogen content, as a raw material to prepare photoluminescent nitrogen-doped carbon dots through one-pot hydrothermal synthesis, and found that the as-prepared CDs have a photoluminescence (PL) quantum yield of 13.9%, and display amphoteric properties depending on the pH, are highly photostable, have low toxicity and are suitable for bioimaging.