Herein, we disclose the utilisation of iodonium ylides to access a range of boron dienolates. Heating of acyclic iodonium ylides in the presence of different aryl boranes leads to the formation of rare 1,3-carboboration products. This methodology could not be expanded to cyclic iodonium ylides which instead formed a Lewis acid-base adduct. Products proved to be remarkably stable under a wide range of conditions allowing for their long term storage.
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http://dx.doi.org/10.1039/c9cc08749d | DOI Listing |
J Org Chem
January 2025
School of Traditional Chinese Medicine, Southern Medical University, Guangzhou 510515, China.
The first Ru(II)-catalyzed C-H activation/[4 + 2] annulation of aryl imidates with heteroaromatic iodonium ylides is reported. Our approach features the utilization of a commercially available ruthenium catalyst, providing a one-step construction of phelligridin analogues from easily available and nonpreactivated starting materials. The developed methodology is successfully employed for the total synthesis of phelligridin A, significantly streamlining previous multistep synthesis.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Traditional Chinese Medicine, Southern Medical University, Guangzhou 510515, P. R. China.
To date, a general approach for the direct α-acyloxylation of cyclic 1,3-dicarbonyls remains challenging. Herein, we report a Pd-catalyzed α-acyloxylation of cyclic 1,3-dicarbonyl-derived hypervalent iodine compounds with highly abundant carboxylic acids. Our approach utilizes a commercially available Pd(OAc) catalyst, which exhibits mild reaction conditions, scalability, operational simplicity, and robustness against moisture and air.
View Article and Find Full Text PDFBeilstein 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 PDFChemistry
January 2025
Deparment of Radiology & Nuclear Medicine, Amsterdam UMC, location Vrije Universiteit Amsterdam, De Boelelaan 1117, 1081 HV, Amsterdam, The Netherlands.
Fluorine-18 is the predominant radionuclide used to label Positron Emission Tomography (PET) tracers. One outstanding challenge in nucleophilic aromatic radiofluorination reactions is the sensitivity of precursors and catalysts for basic reaction conditions, which are necessary for the work-up of [F]fluoride, resulting in limited reproducibility. Triflyl [F]fluoride is a new [F]fluoride source that allows freedom in choice of type and amounts of base and cryptand.
View Article and Find Full Text PDFChem Commun (Camb)
November 2024
School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University, Zhongshan 528458, P. R. China.
The present work reveals a new metal-catalyzed synthetic reaction involving 1,2,3-benzotriazinones with carbonyl sulfoxonium ylide and iodonium ylide, resulting in divergent products. Within this catalytic system, 3-phenylbenzo[][1,2,3]triazin-4(3)-one derivatives undergo C-H alkylation processes facilitated by a Cp*Rh(III) catalyst when combined with a carbonyl sulfoxonium ylide. On the other hand, when iodonium ylide substrates are used, they undergo an alkenylation reaction facilitated by a Cp*Ir(III) catalyst.
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