Organocatalytic diastereo- and atroposelective construction of N-N axially chiral pyrroles and indoles.

The construction of N-N axially chiral motifs is an important research topic, owing to their wide occurrence in natural products, pharmaceuticals and chiral ligands. One efficient method is the atroposelective dihydropyrimidin-4-one formation. We present herein a direct catalytic synthesis of N-N atropisomers with simultaneous creation of contiguous axial and central chirality by oxidative NHC (N-heterocyclic carbenes) catalyzed (3 + 3) cycloaddition. Using our method, we are able to synthesize structurally diverse N-N axially chiral pyrroles and indoles with vicinal central chirality or bearing a 2,3-dihydropyrimidin-4-one moiety in moderate to good yields and excellent enantioselectivities. Further synthetic transformations of the obtained axially chiral pyrroles and indoles derivative products are demonstrated. The reaction mechanism and the origin of enantioselectivity are understood through DFT calculations.

Regiospecific construction of m-alkenyl benzaldehyde from ß-bromoenal and vinyl borate.

Herein, we report a Pd-catalyzed regiospecific cycloaromatization of ß-bromoenal and vinyl borate esters to synthesize m-alkenyl substituted benzaldehydes. This allows the construction of complex molecules from simple materials, which may be useful in the search for new optical materials.

Cascade 8π Electrocyclization/Benzannulation to Access Highly Substituted Phenylpyridines.

A cascade 8π electrocyclization/benzannulation reaction was developed to obtain the synthetically important highly substituted phenyl-pyridines. This method shows great potential in the rapid and inexpensive application of the scalable and operationally simple production of accessible substrates. On the basis of the resulting phenyl-pyridine products, a new Ru catalyst and bidentate ligand were designed and prepared, further demonstrating its high practicability.

Divergent Synthesis of Highly Substituted Pyridines and Benzenes from Dienals, Alkynes, and Sulfonyl Azides.

Divergent synthesis is extremely important for the highly efficient preparation of structurally diverse target molecules. Herein, we describe a multicomponent cascade reaction, which allows access to highly substituted pyridines and benzenes by combining four individual steps in a one-pot manner from the same set of readily available starting materials. The azepine intermediates were first used as the precursors for 6π-electrocyclization to construct highly substituted pyridines and benzenes in a tunable manner.

Copper and Rhodium Relay Catalysis for Selective Access to cis-2,3-Dihydroazepines.

A new catalytic protocol to access synthetically challenging cis-2,3-dihydroazepines is reported. The reaction starts with readily available dienals, alkynes, and sulfonyl azides as the substrates and employs copper and rhodium as relay catalysts. Key steps include a copper-catalyzed reaction between an alkyne and a sulfonyl azide to form a triazole intermediate. The subsequent activation of this triazole intermediate by a rhodium catalyst, followed by a reaction with the dienal substrate, eventually leads to the dihydroazepine product. The regio- and stereochemistries of the products are believed to be controlled through a stereospecific conrotatory 8π-electrocyclization process against a possible competing 6π-electrocyclization process.

Europium(III) modified silicone nanoparticles for ultrasensitive visual determination of tetracyclines by employing a fluorescence color switch.

Silicon nanoparticles (SiNPs) modified with Eu(III) were synthesized and are shown to be a viable ratiometric fluorescent probe for tetracycline antibiotics. SiNPs/Eu under 405 nm excitation display two emissions, viz. a strong cyan colored fluorescence peaking at 497 nm and a weak pink fluorescence peaking at 622 nm. On addition of tetracyclines (chlortetracycline, tetracycline, doxycycline), the fluorescence at 497 nm is reduced, while the one at 622 nm is increased. Thus, the visible color of fluorescence changes from cyan to pink. This was exploited to design ratiometric fluorometric method for detecting tetracyclines. The method has a limit of detection that is lower by a factor of about 1000 when compared to the use of SiNPs only. A test paper was prepared with the SiNPs/Eu and then applied for the visual semi-quantitative detection of tetracyclines. With the addition of tetracyclines, the test paper exhibited a dosage-sensitive color conversion from cyan to pink with a visually discernible scale as low as 0.4 µM. Graphical abstract Tetracyclines decrease the fluorescence at 497 nm of europium (III) modified silicon nanoparticles (SiNPs/Eu) due to the inner filter effect and increase the one at 622 nm due to an antenna effect. Thus the fluorescence color of SiNPs/Eu changes from cyan to pink. Based on this color switch, a ultrasensitive and visual determination strategy for tetracyclines is proposed.

[Cloning and expression of Treponema pallidum antigen TpN17 and an epitope of TpN44.5 and clinical application].

OBJECTIVE: To investigate the cloning and expression of Treponema pallidum (TP) specific antigen TpN17 and an epitope of TpN44.5 and the clinical application of this fusion antigen. METHODS: TpN17 gene was amplified from the genome of TP and an epitope of TpN44.5 was spliced to the 5' end of TpN17 gene. This modified TpN17 gene was cloned into the expression vector pGEX4T-2. The recombinant fusion antigen was purified by affinity chromatography and then an enzyme-linked immunosorbent assay (ELISA) kit was prepared. With this kit, the sera of 10 normal persons and 10 TP patients were tested. RESULTS: The molecular weight of the purified fusion antigen was 45,000. Tested with ELISA, 10 serum samples of the TP patients were positive and another 10 of the normal persons were negative. ELISA equipped with the GST-epi-TpN17 antigen showed higher sensitivity and specificity as compared with routine methods. CONCLUSION: The recombinant fusion TP specific antigen GST-epi-TpN17 was suitable for the preparation of ELISA kit in clinical examinations.