A broad range of aliphatic, aromatic, and heterocyclic boronic acids were successfully homologated using trifluorodiazoethane in the presence of BINOL derivatives to provide the corresponding chiral trifluoromethyl containing boronic acid derivatives in high yields and excellent enantioselectivity. The in situ conversion of the chiral transient boronic acids to the corresponding alcohols or β-CF3 carboxylates are also demonstrated.
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Molecules
December 2024
School of Chemistry, South China Normal University, Guangzhou Key Laboratory of Analytical Chemistry for Biomedicine, GDMPA Key Laboratory for Process Control and Quality Evaluation of Chiral Pharmaceuticals, Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006, China.
Oxazoles are important five-membered heterocycles that contain both nitrogen and oxygen atoms. Due to their wide range of biological activities, many oxazoles demonstrate potential for extensive application in various fields, including medicinal chemistry. Trifluoromethyl carbinol, an important pharmacophore, contains both trifluoromethyl and hydroxyl groups and is common in molecules with important biological activities.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Basic Pharmacology of Ministry of Education and Joint International Research Laboratory of Ethnomedicine of Ministry of Education, School of Pharmacy, Zunyi Medical University, Zunyi 563003, China.
We report an efficient, metal-free method for late-stage rapid [F]trifluoromethyl radiolabeling of terminal alkenes at room temperature. Utilizing 3,3-difluoroallyl sulfonium salts as precursors, the process achieves high radiochemical yields (up to 94 ± 2%) in just 30 s, with excellent functional group tolerance. This method offers a simplified and efficient pathway to produce [F]trifluoromethylated terminal alkene compounds, enabling their application in PET imaging and expanding the chemical space for drug discovery.
View Article and Find Full Text PDFJ Org Chem
December 2024
Pharmaceutical Research Institute, Wuhan Institute of Technology, Wuhan 430205, P. R. China.
We report, for the first time, a visible-light-promoted Markovnikov hydroalkoxylation of α-trifluoromethyl alkenes with 1,2-diketones. This transformation proceeded smoothly in the presence of a tertiary amine (EtN), providing a series of enol ethers containing the trifluoromethylated tetrasubstituted center in moderate to excellent yields. In this protocol, hydrogen atom transfer between this amine and 1,2-diketone substrate affords a ketyl radical and an α-aminoalkyl radical, which engages in the formation of a radical anion of the α-CF alkene via a single electron transfer.
View Article and Find Full Text PDFChempluschem
November 2024
Division of Organic Chemistry, Centre of Molecular and Macromolecular Studies Polish Academy of Sciences, Sienkiewicza 112, 90-363, Łódź, Poland.
An unexpected course of the reaction of hexafluorocumyl alcohol dilithium derivative 2 with N-(t-butylsulfenyl)phthalimide (3) has been presented. The process proceeded under mild conditions and resulted in previously undescribed chiral spiro-system- 3',3'-bis(trifluoromethyl)-3H,3'H-1,1'-spirobis(isobenzofuran)-3-one (5) as the only product. A detailed spectral analysis of the product has been provided, and mechanistic aspects have been investigated.
View Article and Find Full Text PDFChirality
December 2024
School of Science, Tianjin Key Laboratory of Molecular Optoelectronic Science, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, China.
Inclusion complexation, hydrogen bonds, π-π interaction, dipole-dipole interaction, and steric hindrance effect all contribute to the enantioseparation ability of cyclodextrin (CD) or CD derivatives. In this work, one native cationic CD chiral stationary phases (SHCDCSP) and four derivatized CD-CSPs, namely, per(4-trifluoromethyl) phenylcarbamoylated-β-CD CSP (SFPhCDCSP), per(4-chloro) phenylcarbamoylated-β-CD CSP (SCPhCDCSP), per(4-bromo) phenylcarbamoylated-β-CD CSP (SBPhCDCSP), and per(4-methyl) phenylcarbamoylated-β-CD CSP (SMPhCDCSP), were prepared via thioether linkage and applied for the enantioseparation of chiral lactides and chiral diketones in both reverse phase (RP) and normal phase (NP) modes. Most of the studied chiral lactides were found to be well resolved (R > 1.
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