This account summarizes how we performed the intramolecular nucleophilic substitutions of the hydroxy groups at alpha-position to trifluoromethyl group. The origin of the steric hindrance of the trifluoromethyl group was found to be the electrostatic repulsive force between the nucleophile and the negatively charged fluorine atoms.

Download full-text PDF

Source
http://dx.doi.org/10.1002/chir.10160DOI Listing

Publication Analysis

Top Keywords

trifluoromethyl group
12
stereospecific substitution
4
substitution alpha-carbon
4
alpha-carbon trifluoromethyl
4
group application
4
application optically
4
optically active
4
active fluorinated
4
fluorinated amino
4
amino acid
4

Similar Publications

Cytotoxic Activity of Bisphosphonic Derivatives Obtained by the Michaelis-Arbuzov or the Pudovik Reaction.

Pharmaceuticals (Basel)

January 2025

Department of Organic Chemistry and Technology, Faculty of Chemical Technology and Biotechnology, Budapest University of Technology and Economics, Műegyetem rkp. 3, 1111 Budapest, Hungary.

Methylenebisphosphonic derivatives including hydroxy-methylenebisphosphonic species may be of potential biological activity, and a part of them is used in the treatment of bone diseases. Methylenebisphosphonates may be obtained by the Michaelis-Arbuzov reaction of suitably α-substituted methylphosphonates and trialkyl phosphites or phosphinous esters, while the hydroxy-methylene variations are prepared by the Pudovik reaction of α-oxophosphonates and different >P(O)H reagents, such as diethyl phosphite and diarylphosphine oxides. After converting α-hydroxy-benzylphosphonates and -phosphine oxides to the α-halogeno- and α-sulfonyloxy derivatives, they were utilized in the Michaelis-Arbuzov reaction with trialkyl phosphites and ethyl diphenylphosphinite to afford the corresponding bisphosphonate, bis(phosphine oxide) and phosphonate-phosphine oxide derivatives.

View Article and Find Full Text PDF

Organofluorines, particularly those containing trifluoromethyl (CF3) groups, play a critical role in medicinal chemistry. While trifluoromethylation of alkenes provides a powerful synthetic route to construct CF3-containing compounds with broad structural and functional diversity, achieving enantioselective control in these reactions remains a formidable challenge. In this study, we engineered a nonheme iron enzyme, quercetin 2,3-dioxygenase from Bacillus subtilis (BsQueD), for the enantioselective trifluoromethylazidation of alkenes.

View Article and Find Full Text PDF

Multifunctional Polar Polymer Boosting PEO Electrolytes toward High Room Temperature Ionic Conductivity, High-Voltage Stability, and Excellent Elongation.

ACS Appl Mater Interfaces

January 2025

International Science and Technology Cooperation Base of Energy Materials and Application, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, P.R. China.

Poly(ethylene oxide) (PEO) has been widely studied as an electrolyte owing to its excellent lithium compatibility and good film-forming properties. However, its electrochemical performance at room temperature remains a significant challenge due to its low ionic conductivity, narrow electrochemical window, and continuous decomposition. Herein, we prepare a multifunctional polar polymer to optimize PEO's electrochemical properties and cycling stability.

View Article and Find Full Text PDF

Mild [3 + 3] Annulation of (Trifluoromethyl)alkenes with Thioureas Enabled by Chemoselective Defluorinative Amination: Synthesis of 6-Fluoro-3,4-dihydropyrimidine-2(1)-thiones.

J Org Chem

January 2025

School of Chemistry and Chemical Engineering, Key Laboratory of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou 510640, China.

The chemoselective defluorinative [3 + 3] annulation of (trifluoromethyl)alkenes with thioureas is reported. This protocol affords various attractive 6-fluoro-3,4-dihydropyrimidine-2(1)-thiones in high yields, features transition-metal free, mild conditions, efficient, is operationally simple and gram-scalable, tolerates diverse useful functional groups.

View Article and Find Full Text PDF

The emergence of RNA viruses driven by global population growth and international trade highlights the urgent need for effective antiviral agents that can inhibit viral replication. Nucleoside analogs, which mimic natural nucleotides, have shown promise in targeting RNA-dependent RNA polymerases (RdRps). Starting from protected 5-iodouridine, we report the synthesis of -substituted-(1,3-diyne)-uridines nucleosides and their phosphoramidate prodrugs.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!