Chinese Journal of Chemistry最新文献

As the aza-isosteres of sulfonyl fluorides, sulfonimidoyl- and sulfondiimidoyl fluorides are versatile and robust SuFEx linkage agents, yet with limited synthetic accessibility. Herein, we report the straightforward, divergent synthesis of sulfonimidoyl- and sulfondiimidoyl fluorides from bench-stable, readily available sulfenamides and Selectfluor. The obtained sulfonyldiiminyl fluorides readily underwent versatile SuFEx reactions with various nucleophiles to afford various biologically interesting sulfondiimidoyl derivatives.

RNA modifications have revealed essential regulatory roles in messenger RNA (mRNA) metabolism to affect cellular gene regulation, and have also received widespread applications in RNA therapeutics such as mRNA vaccine and protein replacement. Most efforts focus on mRNA internal base and ribose modifications, however, chemical modification within mRNA poly(A) tail remains unexplored. In this work, we synthesized luciferase and GFP (Green Fluorescent Protein) mRNAs with a fully chemically modified poly(A) tail, in which adenosine is replaced by either base-modified N⁶-methyladenosine (m⁶A)/N⁶-ethyladenosine (Et⁶A) or ribose-modified 2’-O-methyladenosine (Am), and investigated the effect of these tail modifications on mRNA stability and translation efficiency upon transfection into cells using fluorescent and chemiluminescent reporter assays. The results showed that all these modifications impaired translation without affecting mRNA stability. Further study demonstrated that modified poly(A) tail weakens its binding to PABPC1 (Polyadenylate-Binding Protein 1), which reduces the formation of mRNA head-to-tail loop and thus decreases the translation efficiency. Our finding reveals the translation-regulatory role of the adenosine modifications within poly(A) tail, offering a new way for manipulating mRNA translation inside cells.

We report a transition-metal-free and bis(pinacolato)diborane (B₂Pin₂)-promoted transfer hydrogenation of various alkynes to alkanes in high yields with methanol as hydrogen source under mild reaction conditions. Control experimental results revealed that bis(pinacolato)diborane and methanol played important roles for the transfer hydrogenation of alkynes to alkanes. It is shown that in situ generated borane was the key reductant for the activated alkynes whereas bis(pinacolato)diborane served as strong Lewis acid reagents for diarylacetylenes. More importantly, these transfer hydrogenations could be applied into modifying natural products and a CF₃-substituted alkyl group could be easily introduced into complex molecules. The present method highlights mild reaction conditions, broad substrate scope of alkynes, transition-metal free transfer hydrogenation, and gram scalable preparations without column chromatography.

Given the ubiquity of amines in natural products, pharmaceuticals, and functional materials, the development of facile deamination methods offers a promising strategy to increase the diversity of chemicals in drug discovery. In this study, we design and synthesize a novel deamination reagent, N-(benzyloxy)-N-(isobutyryloxy)-4-nitrobenzamide, leveraging its unique properties to efficiently convert readily available primary amines into diverse aromatic and heteroaromatic compounds, aliphatic hydrocarbons, and alkyl esters. This method exhibits broad functional group tolerance, including carbonyl, alkynyl, and amino groups, and has been successfully applied to amino acids, peptides and marketed drugs. Furthermore, the scalability of the reaction, as well as its utility in the sequential functionalization/deamination modification and deutero-deamination of various primary amines, highlights the practical potential of this approach.

Alkylamines play an important role in medicinal chemistry, while carboxylic acids are commonly found in many natural products and pharmaceuticals. In this study, we developed a direct photoredox-catalyzed decarboxylative amination of alkyl carboxylic acids using a novel N-centered radical scavenger. This method avoids pre-activation and transition-metal catalysts, allowing a diverse range of readily available carboxylic acids to be efficiently converted into medicinally valuable amines. Further mechanistic studies and DFT calculations were conducted to provide evidence for the proposed photoredox-catalyzed pathway. This protocol is operationally simple and has excellent functional group compatibility, which is likely to be of great use in synthetic chemistry