TBN-triggered, manipulable annulations of o-hydroxyarylenaminones for divergent syntheses of oximinochromanones and oximinocoumaranones.

Divergent synthesis provides an indispensable route to rapid acquisition of structurally diverse chemical scaffolds from identical starting materials. Herein, we describe unprecedented divergent annulations of o-hydroxyarylenaminones promoted by tert-butyl nitrite (TBN) under mild conditions. Two different types of benzo-oxa-heterocycle, including oximinochromanones and oximinocoumaranones, were smoothly assembled with a broad substrate scope and good functional group compatibility.

Photocatalytic Hydroacylation of Alkenes by Directly Using Acyl Oximes.

Acyl oximes are directly used as the acyl radical precursors in the hydroacylation reactions for the first time. In this work, acyl radicals can be effectively generated via ß-scission of a phosphoranyl radical under photocatalytic conditions. As a result, the hydroacylation of alkenes triggered by the resulting acyl radicals leads to facile syntheses of a range of valuable ketones.

A One-Pot Ring-Opening/Ring-Closure Sequence for the Synthesis of Polycyclic Spirooxindoles.

One-pot ring-opening/ring-closure process of combining methyleneindolinone with 3-aminooxindole has been developed in this work. Novel polycyclic spirooxindoles were efficiently assembled under mild conditions in high yields (up to 95 %) with moderate to good diastereoselectivities (up to >95:5 d.r.) through simple filtration.

Organocatalytic Domino Entry to an Octahydroacridine Scaffold Bearing Three Contiguous Stereocenters.

A facile and enantioselective access to a functionalized octahydroacridine scaffold was developed via an organocatalytic domino sequence between cyclohexenone and 2- N-substituted benzaldehyde. High levels of yields (up to 99%) and enantioselectivities (up to 99:1 er) were readily achieved in this developed organocatalytic transformation, which holds promising applications in the construction of complex multicyclic systems for further pharmacological studies.

Visible-Light-Induced External Radical-Triggered Annulation To Access CF2-Containing Benzoxepine Derivatives.

A facile and diversified synthesis of functionalized CF2-containing benzoxepine derivatives via photoredox catalysis was achieved in this work. This novel protocol features broad substrate scope, mild reaction conditions, operational simplicity, easy scale-up, and versatile derivatization, which would facilitate its practical and broad applications in the construction of valuable and synthetically challenging heterocycles.

Solvent-Minimized, Chromatography-Free, Diastereoselective Synthesis of Oxazolidine-Dispirooxindoles via oxa-1,3-Dipolar Cycloaddition of 3-Oxindole.

An efficient and diastereoselective decarboxylative oxa-1,3-dipolar cycloaddition between 3-oxindoles and diverse amino acids is developed to access novel oxazolidine-dispirooxindole skeletons bearing vicinal quaternary carbon centers. This protocol features operational simplicity, a broad substrate scope, and good to excellent chemical yields and diastereoselectivities. In particular, minimal solvent (1 mL/10 mmol) and chromatography-free purification render this synthetic process more efficient and environmentally benign in the context of green chemistry.

Organocatalytic Asymmetric Allylic Alkylation of Morita-Baylis-Hillman Carbonates with Diethyl 2-Aminomalonate Assisted by In Situ Protection.

With the aid of in situ protection by N-(2-formylphenyl)-4-methyl-benzenesulfonamide, enantioselective allylic alkylation of Morita-Baylis-Hillman carbonates with diethyl 2-aminomalonate was successfully realized. The corresponding adducts can be obtained in up to 99% yield with up to 98% ee as well as excellent regioselectivity. Besides, the adducts with opposite configurations were readily prepared by utilizing easily available and inexpensive quinine or quinidine as organocatalyst. Facile deprotection of the resulting adduct provides straightforward access to enantiopure α-methylene-γ-lactam.

Diversity-driven and facile 1,3-dipolar cycloaddition to access dispirooxindole-imidazolidine scaffolds.

A diversity-driven three-component 1,3-dipolar cycloaddition of isatins, amino acids and isatin-derived ketimines was developed to facilely assemble dispirooxindole-imidazolidine skeletons bearing vicinal quaternary carbon centers. This protocol features additive-free, minimal solvent usage (0.1 mL DMSO/0.2 mmol scale), wide substrate scope (34 examples), mild reaction conditions (room temperature) and high chemical yield (up to 99%).

Expression of caveolin-1 is correlated with lung adenocarcinoma proliferation, migration, and invasion.

Both tumor suppressor and tumor promoter roles, which are dependent on the tumor type, have been described for caveolin-1 (CAV-1). Because CAV-1 can modulate cell signaling, we tested the hypothesis that it regulates lung adenocarcinoma cell proliferation and metastasis via modulation of epidermal growth factor receptor (EGFR) activity. The lung adenocarcinoma cell line, GLC-82, was transfected with pcDNA3.1CAV-1 plasmid, before cell proliferation, migration, and invasion were analyzed. In the in vivo xenograft model, the relationship between the CAV-1 expression and EGFR phosphorylation and signaling was assessed by western blot analysis. The relationship between the CAV-1 as well as Ki67 expression and the clinicopathological characteristics of 68 lung adenocarcinoma patients was also examined using immunohistochemistry. Overexpression of CAV-1 significantly increased GLC-82 proliferation (p < 0.001), migration (p < 0.001), and invasion (p = 0.002) as well as EGFR and ERK phosphorylation (p < 0.05). The GLC-82/CAV-1 cell tumors were also significantly larger than those of control cells (all p ≤ 0.05). In lung adenocarcinoma patients, CAV-1 expression was positively correlated with lymph node metastasis and cancer stage. Finally, CAV-1 expression was associated with the expression of Ki-67, a marker of cell proliferation. CAV-1 enhanced GLC-82 cell proliferation, migration, and invasion possibly through EGFR and ERK signaling. Furthermore, the relationship of CAV-1 with Ki67 expression, a marker of proliferative capacity, in lung adenocarcinoma samples is suggestive of its role in disease progression. Further studies are required to confirm the role of CAV-1 in the metastasis of lung adenocarcinoma as well as its potential prognostic and therapeutic value.

Dibromido(2,2':6',2''-terpyridine-κN,N',N'')zinc(II).

In the title compound, [ZnBr(2)(C(15)H(11)N(3))], the Zn(II) ion is five-coordinated by the three N atoms from a 2,2':6',2''-terpyridine ligand (terpy) and two bromide anions in a distorted trigonal bipyramidal configuration. Each mol-ecule is situated on a twofold rotational axis that passes through the Zn(II) ion and the central ring of the terpy ligand. In the crystal structure, aromatic π-π inter-actions between terpy ligands [centroid-centroid distances = 3.6265 (9) Å] link mol-ecules into stacks propagated in the [001] direction.

Tetra-aqua-(5,5'-dimethyl-2,2'-bipyridine-κN,N')zinc(II) sulfate.

The asymmetric unit of the title compound, [Zn(C(12)H(12)N(2))(H(2)O)(4)]SO(4), consists of a Zn(II) complex cation, a sulfate anion and four mol-ecules of water coordinated to the Zn(II) atom. The Zn(II) complex cation, with approximate twofold symmetry, displays a slightly distorted octa-hedral geometry around the Zn(II) atom, which is coordinated by two N atoms from a 5,5'-dimethyl-2,2'-bipyridine ligand and by the O atoms of four water mol-ecules. In the crystal, O-H⋯O hydrogen bonds help to establish the packing.

[Clinical analysis of 71 cases of multiple primary cancers in head and neck squamous carcinomas].

OBJECTIVE: To study the location, treatment, life status of multiple primary cancers (MPCs) in head and neck squamous cell carcinomas. METHODS: The clinical data of 71 head and neck squamous carcinoma patients with MPCs were retrospectively analyzed. RESULTS: MPCs were seen in head and neck regions in 27 cases and in remote organs in 42 cases, two of which were triplicate primary cancers. Four cases were synchronous MPCs, including one patient with synchronous triplicate primary cancer. Other 67 cases were heterochronous MPCs, including one patient with heterochronous triplicate primary cancer. Of 67 heterochronous MPCs, the time interval between index tumor presentation and diagnosis of MPCs was eight months to twelve years. MPCs occurred in seventy percent index oral cavity squamous cancers, which were located in head and neck regions, and in sixty-two percent index hypopharynx cancers and seventy-nine percent index laryngeal cancers, which were located in remote organs. The incidence of MPCs in esophagus and lung was higher than that in other remote organs. Among the various MPCs in this serials, the incidence of the disease appeared to be the highest in esophagus, accounting for twenty-four percent of all cases. The total three- and five-year survival rates were 32.4% and 22.5%, respectively. Of all MPCs patients, the three-year survival rate for patients who received different therapies for their MPCs was obviously higher than that of untreated patients (P < 0.01, Chi-square test). CONCLUSIONS: Esophageal carcinoma is the most common second primary cancer among the various MPCs of the head and neck squamous carcinomas. Oral cavity cancers tend to have more MPCs in the head and neck regions, and laryngeal and hypopharyngeal cancers are easily to be associated with MPCs in the remote organs. Regular follow-up and early diagnosis with effective treatment can help to improve the survival of MPC patients in head and neck squamous cell carcinomas.