Nickel-Catalyzed Suzuki-Miyaura Coupling in Water for the Synthesis of 2-Aryl Allyl Phosphonates and Sulfones.

An operationally simple and green protocol using a NiSO4·6H2O/cationic 2,2'-bipyridyl ligand system as a water-soluble catalyst for the coupling of arylboronic acids with (2-haloallyl)phosphonates and (2-haloallyl)sulfones in water under air was developed. The reaction was performed at 120 °C with arylboronic acids (2 mmol) and (2-haloallyl)phosphonates or sulfones (1 mmol) in the presence of 5 mol % of the Ni catalytic system in a basic aqueous solution for 1 h, giving the corresponding 2-aryl allyl phosphonates or sulfones in good to excellent yields. This reaction features the use of an abundant transition metal as a catalyst in water and exhibits high functional group tolerance, rendering it an eco-friendly procedure.

Iron-Catalyzed Cadiot-Chodkiewicz Coupling with High Selectivity in Water under Air.

An iron-based catalytic system was developed for the cross-coupling of 1-bromoalkynes with terminal alkynes to selectively generate unsymmetrical 1,3-butadiynes in water under air. It was found that a combination of 1-bromoalkynes derived from less acidic terminal alkynes with more acidic counterparts would greatly enhance yields and selectivity for unsymmetrical 1,3-butadiynes. The reaction was also applicable for the synthesis of unsymmetrical 1,3,5-hexatriynes through coupling of 1-bromoalkynes and trimethylsilyl-protected 1,3-butadiynes in a one-pot manner.

Enantioselective vinylogous aldol/lactonization cascade reaction between ß,γ-unsaturated amides and trifluoromethyl ketones: facile access to chiral trifluoromethyl dihydropyranones.

An efficient asymmetric vinylogous aldol/lactonization cascade reaction between ß,γ-unsaturated amides and trifluoromethyl ketones has been developed. Using a chiral cyclohexanediamine-based tertiary amine-thiourea catalyst, optically active trifluoromethyl dihydropyranones have been constructed in moderate-to-excellent yields (up to 99%) with excellent stereoselectivities (96-> 99.5% ee).

Conformational Regulation of Multivalent Terpyridine Ligands for Self-Assembly of Heteroleptic Metallo-Supramolecules.

A two-ligand system composed of the predesigned multivalent and complementary terpyridine-based ligands was exploited to construct heteroleptic metallo-supramolecules and to investigate the self-assembly mechanism. Molecular stellation of the trimeric hexagon [Cd6L23] gave rise to the exclusive self-assembly of the star hexagon [Cd18L16L33] through complementary ligand pairing between the ditopic and octatopic tectons. To understand how the intermolecular heteroleptic complexation influenced the self-assembly pathway, the star hexagon was truncated into two triangular fragments: [Cd12L13L43] and [Cd12L13L53]. In the self-assembly of [Cd12L13L43], the conformational movements of hexatopic ligand L4 could be regulated by L1 to promote the subsequent coordination event, which was the key step to the successful multicomponent self-assembly. In contrast, the formation of [Cd12L13L53] was hampered by the geometrically mismatched intermediates.

One-Pot Self-Assembly of Stellated Metallosupramolecules from Multivalent and Complementary Terpyridine-Based Ligands.

A series of stellated metallosupramolecular architectures have been assembled through three-component integrative self-sorting. Building on the complementary ligand pairing, the initial attempts to synthesize the hexagram complex from a combination of X-shaped tetrakis- and V-shaped bis-terpyridine ligands, and CdII ions, resulted in an unprecedented mixture of stellated octanuclear and dodecanuclear metallocages, which were further isolated by column chromatography. To overcome the unexpected obstacle, the multivalent ligand design along with spontaneous heteroleptic complexation was applied to realization of the one-pot synthesis of the intricate topology. A centrally situated triangle served as a prop for quantitative formation of the six-pointed stellated complex. Notably, in the absence of the triangular prop, a four-pointed star was produced.

Facile synthesis of multicomponent heterobimetallic metallomacrocycles through selective metal-ligand coordination.

Three heterobimetallic metallomacrocycles were readily assembled through either a stepwise or a one-pot protocol by selective complexation of ZnII ions and PdII or PtII acceptors with the predesigned ligands possessing one 60°-bent bisterpyridine and two mono- or bis-pyridines. In the multicomponent self-assembly, the preorganized ZnII-terpyridine metallo-triangle led to the formation of the exterior macrocycles.

Metal-free oxidative coupling of quinoxalin-2(1H)-ones with arylaldehydes leading to 3-acylated quinoxalin-2(1H)-ones.

A facile TBHP-mediated direct oxidative coupling of quinoxalin-2(1H)-ones with arylaldehydes has been developed under metal-free conditions. This method provided a convenient and efficient approach to various 3-acylated quinoxalin-2(1H)-ones from readily available starting materials with excellent regioselectivity. This reaction proceeded efficiently under mild conditions over a broad range of substrates and with functional group tolerance.

miR-128 affects biological behavior of breast cancer cells through the targeting of RECK / 局解手术学杂志

Objective To investigate the biological behavior of breast cancer cells induced by miR-128 targeting RECK and its possible mechanism.Methods The expression of miR-128 in cell lines and transfection efficiency of lentiviral were detected by Western blot.Flow cytometry was used to detect the effect of miR-128 on the apoptosis of breast cancer cells.The dual luciferase assay was used to detect the in-teraction of miR-128 and RECK in breast cancer cells.Flow cytometry was used to detect the reversal effect of RECK on miR-128 in the cell cycle and colony formation of breast cancer cells.Results The expression of miR-128 in MCF-7 cells was 3.05 times that of NC cells,and the lentiviral transfection efficiency was obvious.miR-128 inhibits the growth of MCF-7 cells by inducing apoptosis and inhibiting cell cycle progression.RECK was the direct target of miR-128,and miR-128 directly regulated the expression of RECK.RECK ectopic recovery,miR-128 on breast cancer cell apoptosis and cell cycle inhibition had also been partially restored.Conclusion miR-128 plays an important role in the development and progression of breast cancer.It can interact with RECK to regulate the biological behavior of breast cancer cells,which suggests that miR-128 and RECK may be the potential therapeutic targets of breast cancer.

Enantioselective direct vinylogous aldol-cyclization cascade reaction between ß,γ-unsaturated amides and o-quinones.

1,2-Diketones are employed, for the first time, as electrophiles in the vinylogous aldol reaction. With 5 mol% of chiral tertiary amine-thiourea , a direct vinylogous aldol-cyclization cascade reaction between ß,γ-unsaturated amides and o-quinones has been achieved to produce spirocyclic dihydropyranones in 76-99% yield and 82-95% ee.

Metallo-Supramolecular Self-Assembly of a Multicomponent Ditrigon Based on Complementary Terpyridine Ligand Pairing.

Predesigned complementary complexation of two 2,2':6',2″-terpyridine-based ligands was established by installing 2,6-dimethoxyphenyl substituents at the terpyridyl 6,6″-positions, which provided ancillary ion-dipole interactions in the coordination process and extra π-stacking stabilization in the resultant heteroleptic complex. The high-fidelity self-recognition ligation afforded facile access to the quantitative self-assembly of multicomponent triangle [Cd6L(3)3L(4)3] and ditrigon [Cd15L(3)6L(5)3] (that is, a hexagon with six 120° angles and two alternating edge lengths). It was found that the linear 6,6″-substituted ditopic motif (L(3)) would be directed by the ligand geometry of L(5) to selectively incorporate into the parallel homoleptic connections in the bilayered framework.

Facile Self-Assembly of Metallo-Supramolecular Ring-in-Ring and Spiderweb Structures Using Multivalent Terpyridine Ligands.

A series of metallo-supramolecular ring-in-ring structures was generated by assembling Cd(II) ions and the multivalent terpyridine ligands (L(1-3)) composed of one 60°-bent and two 120°-bent bis(terpyridine)s with varying alkyl linker lengths. The mechanistic study for the self-assembly process excluded an entropically templated pathway and showed that the intramolecularly complexed species is the key intermediate leading to ring-in-ring formation. The next-generation superstructure, a spiderweb, was produced in quantitative yield using the elongated decakis(terpyridine) ligand (L(5)).

Copper-catalyzed domino coupling reaction: an efficient method to synthesize oxindoles.

An efficient and novel procedure for a copper catalyzed domino coupling reaction has been developed, which afforded various oxindoles in good to excellent yields with tolerance of various substituents. In addition, this method could be applied to synthesize horsfiline and coerulescine in few steps with high total yields.