Organic & Biomolecular Chemistry最新文献

In this work, we present the synthesis of a series of l-thiorhamnosyl donors containing O-carbamate protective groups and the study of their influence on the selectivity in rhamnosylations. It is found that a carbamate on the C-4 position increased the β selectivity compared with carbamates on the C2 or C3 positions, respectively, and when no carbamate group was installed. In addition it is found that the observed β selectivity was greater when the 4-O carbamate had less electron withdrawing groups on the nitrogen. The influence of using triflic acid catalysis was studied as well and it was found to lower the β-selectivity. In addition a new efficient one step synthesis of selectively 2,4-O-benzylated rhamnosides was established using phase transfer catalysis.

An oxidative radical-promoted carbonylative cyclization strategy for the synthesis of phenanthren-9-(10H)-one frameworks from biaryl enones using aldehydes as the carbonyl radical sources is disclosed. The reaction proceeds through a sequential addition of a carbonyl radical to the olefin followed by cyclization with an aryl ring. The method is further extended to carbamoyl radicals generated from oxamic acids to access the corresponding phenanthrenones with amide functionalities.

A protocol for the synthesis of α-amino-vinylphosphine oxides by phosphinoenamination reaction between alkyl nitriles and phosphine oxides was developed. The combination of Mn(OAc)₂ as a Lewis acid and guanidine as a Lewis base was found to be an efficient catalytic system for this reaction. A series of alkyl nitriles and phosphine oxides are compatible with this conversion, furnishing the desired products in up to 95% yield under mild conditions. Furthermore, this method demonstrates the capability of gram-scale synthesis.

The synthesis of a biologically relevant 2-amino-N3-alkylamido 4-quinazolinone has been accomplished in four steps from commercially available materials using design principles from both modular and divergent synthesis. N3-Alkylation of 2-chloro-4(3H)-quinazolinone using methyl bromoacetate, followed by C2-amination produced a suitable scaffold for introducing molecular diversity. Optimization of alkylation conditions afforded full regioselectivity, enabling exclusive access to the N-alkylated isomer. Subsequent C2-amination using piperidine, pyrrolidine, or diethylamine, followed by amide bond formation using variously substituted phenethylamines, generated fifteen unique 4-quinazolinones bearing C2-amino and N3-alkylamido substituents. These efforts highlight the reciprocal influence of C2 and N3 substitution on functionalization at either position, establish an effective synthetic pathway toward 2,N3-disubstituted 4-quinazolinones, and enable preliminary bioactivity studies while providing an experiential learning opportunity for undergraduate student researchers.

Few synthetic ion transporters have been reported incorporating indole as the core moiety. We have developed a novel bisindole-based transporter capable of efficient transmembrane anion antiport. This system induced cytotoxicity in MCF-7 breast cancer cells via chloride ion homeostasis disruption and the associated ROS generation, mitochondrial membrane depolarization, and lysosomal deacidification.

Ganoderma lucidum, a fungus used in traditional Chinese medicine, is known for its medicinal value attributed to its active components called Ganoderma triterpenoids (GTs). However, the limited isolation rate of these GTs has hindered their potential as promising drug candidates. Therefore, it is imperative to achieve large-scale preparation of GTs. In this study, four GTs were effectively synthesised from lanosterol. The antitumor activity of these GTs was evaluated in vivo. Endertiin B exhibited potent inhibitory activity against breast cancer cells (9.85 ± 0.91 μM and 12.12 ± 0.95 μM). Further investigations demonstrated that endertiin B significantly upregulated p21 and p27 and downregulated cyclinD1 expression, arresting the cell cycle at the G0/G1 phase and inducing apoptosis by decreasing BCL-2 and increasing BAX and BAK levels. Additionally, endertiin B was found to reduce the expression of proteins associated with the PI3K-AKT signaling pathway. To summarize, endertiin B effectively inhibited cell proliferation by blocking the cell cycle and inducing apoptosis through the PI3K-AKT pathway.