Recently, the Botanical Pesticides Research and Development Team from our college published research papers on the synthesis and application of deuterium-labeled compounds, titled "Single Electron Transfer Reductive Deuteration of Acyl Chlorides for the Synthesis of Deuterated Alcohols with a High Deuterium Atom Economy" and "Highly Chemoselective Synthesis of α,α-Dideuterio Amines by the Reductive Deuteration of Thioamides Using Mild SmI2-D2O," in Organic Letters. Li Hengchao, a postdoctoral researcher of our college, is the first author of these papers, while Professor Hu Zhaonong from our college and Professor An Jie from China Agricultural University are the co-corresponding authors. Wang Kemeng, Li Xinxin, Fu Yijing, and other undergraduate students from our college also participated in this research work.
Deuterium is a non-radioactive stable isotope of hydrogen. Deuterium-labeled compounds can be used as isotopic internal standards in pesticide residue detection and as isotopic probe molecules in metabolic and toxicological studies, as well as in the elucidation of biosynthetic pathways. In particular, the introduction of deuterium atoms into drug molecules can improve pharmacokinetic properties, reduce metabolic toxicity, and stabilize drug conformations. Similarly, deuterium-labeled pesticides may extend their half-life, thereby reducing the application amount and frequency, achieving reduced application and increased efficiency; they may also reduce toxicity to non-target organisms by altering metabolic properties. The synthesis method of deuterium-labeled compounds is a major limiting factor for their research and application. The research and development team for botanical pesticides first established a synthesis method for deuterated alcohol compounds based on a novel single-electron transfer reductive deuteration strategy (Organic Letters 2024, 26, 3, 719-723). This method utilizes economical and inexpensive sodium dispersions as electron donors and deuterated ethanol as the deuterium source to achieve selective and efficient synthesis of dideuterated and polydeuterated alcohols, with a deuteration rate of >92% and high atom economy, meeting the needs for application in pesticide science. Furthermore, using inexpensive and readily available thioamides as active precursors, mild samarium diiodide as the reductant, and heavy water as the deuterium source, the team achieved efficient synthesis of dideuterated amine compounds (Organic Letters 2024, https://doi.org/10.1021/acs.orglett.4c03434). This method has a broad substrate scope and can be applied to the synthesis of primary or secondary aromatic or aliphatic deuterated amines, with high regioselectivity and a deuteration rate of >95%. Additionally, this method has been proven to be applicable to the synthesis of deuterated azaheterocyclic compounds, including six- and seven-membered rings, especially tetrahydroquinolines, which are important fragments of agriculturally active molecules. Different numbers and positions of deuterium can be introduced using this method. As key building blocks for pesticide synthesis, the establishment of the aforementioned methods will promote the research and application of deuterated compounds in pesticide science.
Establishment and application of synthesis methods for deuterated alcohol and amine compounds
In addition, Dr. Li Hengchao recently published a research paper titled "SO2F2 mediated click chemistry enables modular disulfide formation in diverse reaction media" in Nature Communications as the first author. Professor An Jie from China Agricultural University is the corresponding author of it, and Professor Hu Zhaonong of our college participated in some parts of this research work. The study proposes a novel SO2F2-mediated click chemistry reaction that achieves efficient and highly selective disulfide bond formation, overcoming the limitations of existing methods. In particular, the preparation and characterization of in situ hydrogels demonstrate the potential application of this method in drug or pesticide sustained-release materials.The aforementioned researches were supported by grants from the China Postdoctoral Science Foundation (GZC20232163), the National Natural Science Foundation of China (32372597), and the National Key Research and Development Program of China (2020YFA0907903).
Original link：https://doi.org/10.1021/acs.orglett.3c04155https://doi.org/10.1021/acs.orglett.4c03434https://www.nature.com/articles/s41467-024-52606-w
