Synthesis of Benzoylacetonitriles from Pd-Catalyzed Carbonylation of Aryl Iodides and Trimethylsilylacetonitrile

Palladium-catalyzed carbonylation of aryl iodides and trimethylsilylacetonitrile to produce benzoylacetonitrile derivatives through a one-pot, three-component reaction is described. This preparation method provides good yields of the carbonylated products without any additional ligands. It has a broad substrate scope with a high tolerance for a variety of functional groups

Additive-Free Decarboxylative Coupling of Cinnamic Acid Derivatives in Water: Synthesis of Allyl Amines

The first example of an additive-free decarboxylative coupling of cinnamic acid derivatives with formaldehyde and amines to afford the corresponding allyl amines is reported. This reaction is highly environmentally friendly because it was conducted in H₂O and without any additives, releasing only CO₂ and H₂O as byproducts. This reaction showed a broad substrate scope including cyclic and acyclic amines and high functional group tolerance. Moreover, phenyl dienoic acid participated in this type of decarboxylative coupling reaction

Base-Mediated Synthesis of Anhydrides from Activated Amides

Symmetrical anhydrides were synthesized from activated amides such as N-benzoylsaccharins and N-Boc-protected benzamides. The activated amides reacted with H2O in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) at 25 °C to produce the corresponding symmetrical anhydrides in high yields through C–N bond cleavage. In addition, N-benzoylsaccharins reacted with benzoic acid derivatives to generate unsymmetrical anhydrides in high yields

Highly Reactive Palladium-Catalyzed and Acetonitrile-Mediated Three-Component Reactions for Arylsulfone Synthesis

Arylsulfone groups play an important role in the synthesis of functionalized molecules. The acetonitrile-mediated three-component reactions for arylsulfone synthesis were developed in the presence of a 0.00025 mol % palladium catalyst. Arylboronic acids reacted with potassium metabisulfite (K2S2O5) and benzyl bromide in the presence of LiF and a very low concentration of PdCl2 in acetonitrile solvents to produce the corresponding benzyl arylsulfones in moderate to good yields. Various arylboronic acids reacted with K2S2O5 and carbon electrophiles to produce the desired arylsulfones under the optimized conditions. It was proposed that acetonitrile accelerated the generation of aryl anion species from the reaction of arylboronic acids and LiF

Selective Synthesis of (<i>E</i>)- and (<i>Z</i>)‑Allyl Nitriles via Decarboxylative Reactions of Alkynyl Carboxylic Acids with Azobis(alkylcarbonitriles)

Allyl nitriles were synthesized from the reactions of arylpropiolic acids with azobis­(alkylcarbonitriles) (AIBN or ACCN). In the presence of Cu­(OAc)₂ as a catalyst and pyridine as the solvent, the (<i>E</i>)-stereoisomer was formed as the major product. This transformation shows good tolerance toward alkoxy, halogen, alcohol, amine, ester, and ketone functional groups. When the reaction was conducted with the sterically bulky amine, ethyldiisopropylamine, in the absence of a copper catalyst, the corresponding (<i>Z</i>)-stereoisomers were formed preferentially

Metal-Free Decarboxylative Three-Component Coupling Reaction for the Synthesis of Propargylamines

A metal-free decarboxylative three-component coupling reaction was developed. When alkynyl carboxylic acids, paraformaldehyde, and amines were reacted in CH₃CN at 65 °C for 3 h, the desired propargylamines were obtained in good yields. This coupling reaction also showed good yield in water solvent. This reaction showed higher selectivity toward alkynyl carboxylic acids than a terminal alkyne

RNA-Seq Analysis Reveals a Negative Role of KLF16 in Adipogenesis

<div><p>In this study, we performed high throughput RNA sequencing at the preadipocyte (D0) and differentiated adipocyte (D7) stages of primary brown preadipocyte differentiation in order to characterize the transcriptional events regulating differentiation and function. Compared to the preadipocyte stage (D0), 6,668 genes were identified as differentially expressed genes (DEGs) with a fold change of ≥ 2.0 at the differentiated adipocyte stage (D7). Several adipogenic genes including peroxisome proliferator-activated receptor-γ (PPARγ) and CCAAT/enhancer-binding protein-α (C/EBPα), and Krüppel-like factor (KLF) family genes were differentially expressed at D0 and D7. Since KLF16 gene expression was downregulated at day 7 and its adipogenic function has not been characterized, we investigated its role in adipogenesis. Knockdown of KLF16 stimulated the differentiation of both brown and 3T3-L1 preadipocytes, and led to increased PPARγ expression. However, overexpression of KLF16 had opposite effects. Furthermore, KLF16 downregulated PPARγ expression in brown adipocytes and inhibited its promoter activity. These results indicate that KLF16 inhibits adipogenesis through downregulation of PPARγ expression.</p></div

Overexpression of KLF16 inhibits adipogenesis of primary brown preadipocytes.

<p>Primary brown preadipocytes were transfected with pCMV-KLF16 and were differentiated in differentiation medium for 7 days. (A) KLF16 expression was determined in KLF16-transfected brown preadipocytes by qPCR. qPCR data are presented as means±SEM from three independent experiments. **<i>P</i>< 0.05 vs. control vector (pCMV). (B) Adipocyte differentiation was assessed by Oil Red O staining and expression of PPARγ and aP2 on D0 and D7. qPCR data are presented as means±SEM from three independent experiments. *<i>P</i>< 0.05 vs. control vector (pCMV).</p

KLF16 binding site is between −1914 and −1910 in the PPARγ promoter.

<p>(A) 5′ serial deletion reporters of PPARγ promoter were transfected into HepG2 cells with pCMV-KLF16, and then luciferase activities were measured. Data are presented as means±SEM from three independent experiments. *<i>P</i>< 0.05 vs. PPARγ-Luc reporter. (B) Putative KLF16 binding site between −1914 and −1910.</p

Effect of Foxs (Foxm1, Foxo6, Foxk2, and Foxs1) on the adipogenesis of brown preadipocytes.

<p>(A) Expression of Foxm1, Foxo6, Foxk2, and Foxs1 in siRNA-transfected primary brown preadipocytes. Primary brown preadipocytes were transfected with siRNA for Foxm1, Foxo6, Foxk2, and Foxs1, and their expression was measured by qPCR (B) Oil red O staining of brown preadipocytes transfected with siRNAs for Foxm1, Foxo6, Foxk2, and Foxs1. Primary brown preadipocytes were transfected with siRNAs for Foxm1, Foxo6, Foxk2, and Foxs1, and were then differentiated in differentiation medium for 7 days. Lipid accumulation was assessed by Oil Red O staining. qPCR data are presented as means±SEM from three independent experiments. *<i>P</i>< 0.05 vs. scramble.</p