Synthesis of Aminoallenes via Selenium-π-Acid-Catalyzed Cross-Coupling of N-Fluorinated Sulfonimides with Simple Alkynes.

The facile synthesis of aminoallenes, accomplished by a selenium-π-acid-catalyzed cross-coupling of an N-fluorinated sulfonimide with simple, non-activated alkynes, is reported. Until now, aminoallenes were difficult to be accessed by customary means, inasmuch as pre-activated and, in part, intricate starting materials were necessary for their synthesis. In sharp contrast, the current study shows that ordinary internal alkynes can serve as simple and readily available precursors for the construction of the aminoallene motif. The operating reaction conditions tolerate numerous functional groups such as esters, nitriles, (silyl)ethers, acetals, and halogen substituents, furnishing the target compounds in up to 86 % yield.

Photocatalytic Aerobic Phosphatation of Alkenes.

A catalytic regime for the direct phosphatation of simple, non-polarized alkenes has been devised that is based on using ordinary, non-activated phosphoric acid diesters as the phosphate source and O2 as the terminal oxidant. The title method enables the direct and highly economic construction of a diverse range of allylic phosphate esters. From a conceptual viewpoint, the aerobic phosphatation is entirely complementary to traditional methods for phosphate ester formation, which predominantly rely on the use of prefunctionalized or preactivated reactants, such as alcohols and phosphoryl halides. The title transformation is enabled by the interplay of a photoredox and a selenium π-acid catalyst and involves a sequence of single-electron-transfer processes.

Growth differentiation factor 15 as a radiation-induced marker in oral carcinoma increasing radiation resistance.

BACKGROUND: Growth differentiation factor 15 (GDF15) is involved in tumor pathogenesis of oral squamous cell carcinoma (OSCC). The aim of this study was an investigation of the potential influence of GDF15 on radioresistance of OSCC cells in vitro. METHODS: Oral squamous cell carcinoma cell lines were irradiated with 0, 2, or 6 Gy, and GDF15 expression in the supernatant per survived cell colony was examined with ELISA. Non-irradiated and OSCC cell lines irradiated with 6 Gy were evaluated for GDF15 expression using immunofluorescent staining. For further investigation of GDF15 effects on radioresistance, a GDF15 knockdown model in a human OSCC cell line was established, and apoptotic activity after radiation was measured using the Caspase-Glo 3/7 system. RESULTS: ELISA and immunofluorescent staining indicated an increased GDF15 expression in 5 OSCC cell lines compared with human gingival epithelial cells. Irradiation with two and six gray resulted in a significant elevation of GDF15 expression per survived cell colony in the irradiated OSCC cell lines (P < 0.001). Furthermore, a dose-dependent expression of GDF15 was seen. Immunofluorescent staining confirmed an elevated GDF15 expression in irradiated OSCC cell lines (n = 10; P ≤ 0.001). Apoptotic activity was significantly increased after irradiation in the GDF15 knockdown group compared with control cells (n = 24; P < 0.001). CONCLUSION: This study describes for the first time the vital role of GDF15 both in tumorigenesis and in radioresistance of OSCC cells. With its anti-apoptotic effects, GDF15 possibly promotes tumor progression and might protect carcinoma cells against irradiation effects. Consequently, GDF15 may be a promising therapeutic target in oral cancer.