1. Natural Products Containing 'Rare' Organophosphorus Functional Groups
Janusz J Petkowski, William Bains, Sara Seager Molecules. 2019 Feb 28;24(5):866. doi: 10.3390/molecules24050866.
Phosphorous-containing molecules are essential constituents of all living cells. While the phosphate functional group is very common in small molecule natural products, nucleic acids, and as chemical modification in protein and peptides, phosphorous can form P⁻N (phosphoramidate), P⁻S (phosphorothioate), and P⁻C (e.g., phosphonate and phosphinate) linkages. While rare, these moieties play critical roles in many processes and in all forms of life. In this review we thoroughly categorize P⁻N, P⁻S, and P⁻C natural organophosphorus compounds. Information on biological source, biological activity, and biosynthesis is included, if known. This review also summarizes the role of phosphorylation on unusual amino acids in proteins (N- and S-phosphorylation) and reviews the natural phosphorothioate (P⁻S) and phosphoramidate (P⁻N) modifications of DNA and nucleotides with an emphasis on their role in the metabolism of the cell. We challenge the commonly held notion that nonphosphate organophosphorus functional groups are an oddity of biochemistry, with no central role in the metabolism of the cell. We postulate that the extent of utilization of some phosphorus groups by life, especially those containing P⁻N bonds, is likely severely underestimated and has been largely overlooked, mainly due to the technological limitations in their detection and analysis.
2. Air-stable aryl derivatives of pentafluoroorthotellurate
Daniel Wegener, Kurt F Hoffmann, Alberto Pérez-Bitrián, Ilayda Bayindir, Amiera N Hadi, Anja Wiesner, Sebastian Riedel Chem Commun (Camb). 2022 Aug 25;58(69):9694-9697. doi: 10.1039/d2cc03936b.
We report on two different sets of air-stable derivatives of pentafluoroorthotellurate containing fluorinated and non-fluorinated aryl groups. The acid cis-PhTeF4OH was obtained in gram scale and further transformed to Ag[cis-PhTeF4O], which was used as a cis-PhTeF4O transfer reagent to obtain [PPh4][cis-PhTeF4O]. Furthermore, the synthesis of trans-(C6F5)2TeF3OH was achieved by a selective hydrolysis of trans-(C6F5)2TeF4 in the presence of KF and subsequent protonation by aHF. Quantum-chemical calculations show a higher acidity and robustness against fluoride abstraction for trans-(C6F5)2TeF3OH compared to cis-PhTeF4OH.
3. Lewis Acid-Catalyzed 2,3-Dihydrofuran Acetal Ring-Opening Benzannulations toward Functionalized 1-Hydroxycarbazoles
Shaoren Yuan, Gabriel Guerra Faura, Hailey E Areheart, Natalie E Peulen, Stefan France Molecules. 2022 Nov 30;27(23):8344. doi: 10.3390/molecules27238344.
The development of a Lewis acid-catalyzed, intramolecular ring-opening benzannulation of 5-(indolyl)2,3-dihydrofuran acetals is described. The resulting 1-hydroxycarbazole-2-carboxylates are formed in up to 90% yield in 1 h. The dihydrofuran acetals are readily accessed from the reactions of enol ethers and α-diazo-β-indolyl-β-ketoesters. To highlight the method's synthetic utility, a formal total synthesis of murrayafoline A, a bioactive carbazole-containing natural product, was undertaken.
![Fmoc-Gly-OH-[2-13C]](https://resource.bocsci.com/structure/175453-19-7.gif)
