10.1055/s-2000-6263
The research focuses on the synthesis of the BC ring-systems of the antitumor agent Taxol (also known as paclitaxel), which is a significant challenge in organic chemistry. The study aims to develop a convergent approach to Taxol's total synthesis, with a key step involving a ring-closing metathesis (RCM) reaction to form the BC ring-system by creating the C9-C10 bond. The researchers utilized various catalysts, including Grubbs' ruthenium complex, Schrock’s molybdenum compound, and Nolan’s catalyst, to facilitate the RCM reactions. They experimented with different substrates, such as silylene 26, acetonide 27, and carbonate 23, to optimize the synthesis process. The study concluded that the RCM reaction could successfully form the eight-membered BC ring-system of Taxol, and that catalyst [RuIm] was the most active among the tested catalysts. Interestingly, the research also revealed an instance where a trans cyclooctene was formed, indicating that RCM does not always proceed to thermodynamic equilibrium with catalysts [Ru] and [Mo], unlike with [RuIm] which yielded the expected cis product. The chemicals used in this process included a range of olefins, alcohols, and protected derivatives, as well as metathesis precursors synthesized through various organic reactions such as Shapiro coupling and cyanohydrin homologation. The study provides valuable insights into the synthesis of complex molecular structures like Taxol and contributes to the field of organic chemistry and drug development.
10.1021/ol7024108
Mamoru Shimizu and Mikiko Sodeoka presents a novel and efficient method for synthesizing carbamates, carbonates, and thiocarbonates using 1-alkoxycarbonyl-3-nitro-1,2,4-triazole (NT) transfer reagents. The study introduces stable crystalline reagents that react rapidly with amines, alcohols, and thiols to produce high-purity products without the need for additional bases or lengthy reaction times. The NT reagents, including Z-NT, Troc-NT, Fmoc-NT, and Teoc-NT, are synthesized from corresponding chloroformates and are shown to be highly stable and easy to handle. The reactions proceed quickly, often within minutes, and the byproduct NT can be easily removed by filtration, allowing for the isolation of pure carbamates without chromatographic purification. The method is particularly effective for the selective protection of nucleobases and the synthesis of various functionalized compounds that are challenging to produce using conventional methods. The study highlights the advantages of these new reagents, such as their stability, ease of handling, and the ability to recycle the byproduct NT, making them a practical and convenient alternative for the preparation of carbamates, carbonates, and thiocarbonates.