Iron-Facilitated Oxidative Radical Decarboxylative Cross-Coupling between α‑Oxocarboxylic Acids and Acrylic Acids: An Approach to α,β-Unsaturated Carbonyls

The first Fe-facilitated decarboxylative cross-coupling reaction between α-oxocarboxylic acids and acrylic acids in aqueous solution has been developed. This transformation is characterized by its wide substrate scope and good functional group compatibility utilizing inexpensive and easily accessible reagents, thus providing an efficient and expeditious approach to an important class of α,β-unsaturated carbonyls frequently found in bioactive compounds. The synthetic potential of the coupled products is also demonstrated in subsequent functionalization reactions. Preliminary mechanism studies suggest that a free radical pathway is involved in this process: the generation of an acyl radical from α-oxocarboxylic acid via the excision of carbon dioxide followed by the addition of an acyl radical to the α-position of the double bond in acrylic acid then delivers the α,β-unsaturated carbonyl adduct through the extrusion of another carbon dioxide

Transition-Metal-Free Oxidative α‑C–H Amination of Ketones via a Radical Mechanism: Mild Synthesis of α‑Amino Ketones

A transition-metal-free direct α-C–H amination of ketones has been developed using commercially available ammonium iodide as the catalyst and sodium percarbonate as the co-oxidant. A wide range of ketone ((hetero)­aromatic or nonaromatic ketones) and amine (primary/secondary amines, anilines, or amides) substrates undergo cross-coupling to generate synthetically useful α-amino ketones. The mechanistic studies indicated that a radical pathway might be involved in the reaction process. The utility of the method is highlighted through a concise one-step synthesis of the pharmaceutical agent amfepramone

PIFA-Mediated Esterification Reaction of Alkynes with Alcohols via Oxidative Cleavage of Carbon Triple Bonds

A metal-free esterification of alkynes via CC triple bond cleavage has been developed. In the presence of phenyl­iodine bis­(tri­fluoro­acetate), a diverse range of alkyne and alcohol substrates undergoes triple bond cleavage to produce carboxylic ester motifs in moderate to good yields. The transformation is proposed to proceed via hydroxy­ethanones and ethane­diones as intermediates on the basis of mechanistic studies and exhibits a broad substrate scope and good functional group tolerance

Kaplan-Meier overall survival curves for 668 patients.

<p>The patients were stratified by the number of metastatic lymph nodes (A), the lymph node ratio (B), or the number of involved lymph node regions (C).</p

Kaplan–Meier progression-free survival curves for 668 patients.

<p>The patients were stratified by the number of metastatic lymph nodes (A), the lymph node ratio (B), or the number of involved lymph node regions (C).</p

Histological and immunohistochemical analysis of prostate cancer cell xenografts in nude mice.

<p>AxdAdB3-F/RGD treatment resulted in more extensive tumor necrosis than AxdAdB-3 (HE staining, original magnification x 200 in top panel, x 400 in middle panel). Immunohistochemical staining of the AxdAdB3-F/RGD-treated tumors detected adenoviral hexon protein (bottom panel, original magnification x 400).</p

Cytopathic effects of RGD-fiber modified adenoviruses.

<p>A, RGD-fiber modified infection capacity of adenoviruses. Western blot analysis of hexon protein expression in mock infection (1) or infection with AxCAlacZ (2) and AxCAZ3-F/RGD (3) in prostate cancer cells. B, Flow cytometric analysis of hexon protein expression in AxCAZ3-F/RGD adenovirus-infected cells or AxCAlacZ adenovirus-infected cells. Data are presented as means ± standard deviation for three independent experiments. **P < 0.01 and N.S., not statistically significant. C, Cytopathic effects of RGD-fiber modified adenoviruses on prostate cancer cells. Cells were infected with AxCAlacZ (diamonds), AxCAZ3-F/RGD (squares), AxdAdB-3 (triangles) and AxdAdB3-F/RGD (circles) at a MOI of 30 for 0, 1, 3, 5, and 7 days and then subjected to a cell viability assay. Data are presented as means ± standard deviation for three independent experiments. **P < 0.01 and N.S., not statistically significant.</p

Expression of CAR and integrins α_vβ₃ and α_vβ₅ in human prostate cancer and normal cell lines.

<p>Cells were grown and immunostained with CAR, integrin α_vβ₃, or α_vβ₅ antibody and then subjected to flow cytometric analysis. Columns, percentages of cells expressing CAR, αvβ3 and αvβ5. Data are presented as means ± standard deviation for three independent experiments.</p

Antitumor effects of RGD-fiber modified adenoviruses in vivo.

<p>Prostate cancer PC3 cells were subcutaneously injected into nude mice. After tumor lesions reached approximately 6–7 mm in size virus was injected into the tumor lesion once a day for three days and the mice were sacrificed at day 28. Tumor volume was measured after animals were treated with viruses (n = 5 per group). Data are presented as mean tumor volume ± standard deviation. **P < 0.005.</p