A broadly applicable method for the trifluoromethylthiolation of methylene C(sp)-H, methine C(sp)-H, α-oxygen C(sp)-H, and formyl C(sp)-H bonds is presented using the decatungstate anion as the sole catalyst. By adjusting the substrate ratio and reaction concentration, this method was applied to 40 examples in good regioselectivities, including the derivatization of natural products. Furthermore, SCF-drug analogues were synthesized by subsequent functionalization of the SCF products, highlighting the importance of this photocatalyzed C-H functionalization.
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http://dx.doi.org/10.1021/acs.orglett.1c01870 | DOI Listing |
Chemistry
November 2024
PhotoGreen Lab, Department of Chemistry, University of Pavia, viale Taramelli 12, 27100, Pavia, Italy.
The oxidation of alcohols to the corresponding carbonyl derivatives has been realized under photoelectrochemical conditions in the presence of tetrabutylammonium decatungstate (TBADT) as the homogeneous photocatalyst. The protocol can be applied to both primary and secondary, benzylic and aliphatic alcohols. The desired products are obtained selectively, skipping the need for purposely added chemical oxidants.
View Article and Find Full Text PDFOrg Lett
July 2024
Hefei National Research Center for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
This paper outlines an innovative three-component coupling strategy for the 1,4-difunctionalization of 1,3-butadiene, utilizing sodium decatungstate (NaDT) as a hydrogen atom transfer (HAT) photocatalyst. The photoinduced process efficiently generates homoallylic amino acid esters with 100% atom economy, employing readily available components under mild reaction conditions. This light-induced protocol eliminates the need for an additional transition metal catalysts, additives, or equivalent reducing agents.
View Article and Find Full Text PDFPhys Chem Chem Phys
April 2024
Department of Applied Materials Science, Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Chiba 277-8589, Japan.
A recent experimental study has reported that decatungstate [WO] can degrade various polyesters in the presence of light and molecular oxygen [Li , , 2023, , 15038]. We apply density functional theory to the photocatalyst-polycaprolactone model complex in acetonitrile solution and elucidate the degradation mechanisms and catalytic cycle. We consider hydrogen atom transfer (HAT) and single electron transfer (SET) mechanisms.
View Article and Find Full Text PDFOrg Biomol Chem
March 2024
Department of Chemistry, CMP Degree College, University of Allahabad, Prayagraj, U.P.-211002, India.
The decatungstate anion (WO) appears to exhibit especially interesting properties as a photocatalyst. Because of its unique photocatalytic properties, it is now recognised as a promising tool in organic chemistry. This study examines recent advances in decatungstate chemistry, primarily concerned with synthetic and, to some degree, mechanistic challenges.
View Article and Find Full Text PDFChem Commun (Camb)
February 2024
Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, ON K1N 6N5, Canada.
The characterization of the triplet state of decatungstate (DT*) and its NIR phosphorescence with lifetimes ∼100 ns in acetonitrile allow the easy determination of rate constants that are key to understanding its role in catalysis. The absence of oxygen quenching can now be understood as the excitation energy of DT* is lower than the energy of singlet oxygen.
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