A variety of cyclic five-membered imides was trifluoromethylated in good to excellent chemical yields using (trifluoromethyl)trimethylsilane CF3SiMe3 under fluoride ion catalysis. The method was successfully applied to the stereoselective synthesis of trifluoromethylated bi- and tricyclic lactams which could serve as precursors for designed thrombin inhibitors.
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http://dx.doi.org/10.1039/b407555b | DOI Listing |
Angew Chem Int Ed Engl
January 2025
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.
J Am Chem Soc
July 2024
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
As one of the most powerful trifluoromethylation reagents, (trifluoromethyl)trimethylsilane (TMSCF) has been widely used for the synthesis of fluorine-containing molecules. However, to the best of our knowledge, the simultaneous incorporation of both TMS- and CF- groups of this reagent onto the same carbon of the products has not been realized. Herein, we report an unprecedented SmI/Sm promoted deoxygenative difunctionalization of amides with TMSCF, in which both silyl and trifluoromethyl groups are incorporated into the final product, yielding α-silyl-α-trifluoromethyl amines with high efficiency.
View Article and Find Full Text PDFAcc Chem Res
March 2024
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China.
ConspectusAs fluorine has played an increasingly important role in modulating the physical, chemical, and biological properties of organic molecules, the selective introduction of fluorine atom(s) or fluorinated moieties into target molecules has become a powerful tool in the development of new pharmaceuticals, agrochemicals, and functional materials. In this context, the difluoromethylene (CF) and difluoromethyl (CFH) groups are of special interest because of their ability to serve as bioisosteres of ethereal oxygen atoms and hydroxyl (OH) and thiol (SH) groups, respectively. Difluorocarbene is one of the most versatile reactive intermediates to incorporate CF and CFH groups; however, before 2006, most of the previously known difluorocarbene reagents suffered from several drawbacks such as using ozone-depleting substances (ODSs), difficult-to-handle reagents, or harsh reaction conditions or having narrow substrate scope and/or low yields.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2023
State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
Although great progress has been made in new electrolytes for lithium metal batteries (LMBs), the intrinsic relationship between electrolyte composition and cell performance remains unclear due to the lack of valid quantization method. Here, we proposed the concept of negative center of electrostatic potential (NCESP) and Mayer bond order (MBO) to describe solvent capability, which highly relate to solvation structure and oxidation potential, respectively. Based on established principles, the selected electrolyte with 1.
View Article and Find Full Text PDFSmall
April 2023
College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou, 310014, China.
In consideration of high specific capacity and low redox potential, lithium metal anodes have attracted extensive attention. However, the cycling performance of lithium metal batteries generally deteriorates significantly under the stringent conditions of high temperature due to inferior heat tolerance of the solid electrolyte interphase (SEI). Herein, controllable SEI nanostructures with excellent thermal stability are established by the (trifluoromethyl)trimethylsilane (TMSCF )-induced interface engineering.
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