We describe the nearly quantitative preparation of phosphorus ylides and the Wittig reaction occurring in the solid sate during high-energy mechanochemical processing. Initial insights into the details of the discovered chemical transformations indicate that high-energy mechanical processing supports the interaction of reacting centers by breaking crystallinity of the reactants and by providing mass transfer without a solvent.
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http://dx.doi.org/10.1021/ja017908p | DOI Listing |
Beilstein J Org Chem
November 2024
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Hypervalent iodine(III) reagents have become indispensable tools in organic synthesis, but gaps remain in the functionalities they can transfer. In this study, a fundamental understanding of the thermal stability of phosphorus-iodonium ylids is obtained through X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Insights into the structural factors affecting thermal stability and potential decomposition pathways will enable the future design and development of new reagents.
View Article and Find Full Text PDFSci Adv
November 2024
Department of Chemistry, Gwangju Institute of Science and Technology, Gwangju 61005, Republic of Korea.
Geminal bromofluoroalkenes are an important subclass of versatile organic interhalide, which can serve as useful synthetic precursors to monofluoroalkenes that are valuable amide group isosteres. Nonetheless, despite the vast advancement of olefination methodologies, the broadly applicable stereoselective synthesis remained elusive for geminal bromofluoroalkenes before our work. In particular, the seemingly straightforward Wittig-type approach with interhalogenated phosphorus ylide has been unsuccessful because of the difficulty in the diastereoselective oxaphosphetane formation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.
We report here a novel family of ylidic P-heteroarenes (P1-P6), structurally featuring unique phosphonium cyclopentadienylide (P-Cp)-fused π-skeletons and synthetically prepared via an unexpected one-pot [2+3]/[3+3] phospha-annulation reaction. While the facile and modular synthesis allows the fine-tuning of their optical absorptions and redox properties, single-crystallographic and theoretical analysis of these P-heteroarenes further reveal that the fusion of P-Cp moiety leads to substantial intramolecular charge-separated features with high ylidic character values of up to 84 %. Benefitted from such dipolar structures, these P-heteroarenes not only allows stepwise electrophilic substitution reaction for further structural π-expansions, but also exhibit excellent nonlinear optical (NLO) responses and optical limiting (OL) performances comparable to or exceed those of C.
View Article and Find Full Text PDFOrg Lett
October 2024
Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan.
Phosphine-promoted unprecedented [3 + 2] annulation reactions via ring expansion by using 2-benzylidene-indane-1,3-diones and diynoates for the synthesis of biologically interesting novel naphthoquinones fused with a five-membered ring bearing a phosphorus ylide up to 78% yield are described. Further ring contraction through [1,5] sigmatropic rearrangement to the spiro indan-1,3-diones by CPBA oxidation was revealed and inferred through oxidation, followed by protonation. The relevant structures were confirmed by single-crystal X-ray diffraction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
Institute of Chemistry, Academia Sinica Taipei, Taiwan, ROC.
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