Center for AIDS Research, Laboratory of Biochemical Pharmacology, Department of Pediatrics, Emory University School of Medicine, Atlanta, Georgia 30322, United States.
Published: December 2017
AI Article Synopsis
Article Abstract
A novel and efficient route for the preparation of (2S)-2-chloro-2-fluorolactone 29 is described. This approach takes advantage of a highly efficient diastereoselective electrophilic fluorination reaction (94% yield; >50:1 dr).
The high potential of non-covalent arene-fluoroarene intermolecular interactions in the design of liquid crystals lies in their ability to strongly promote self-assembly, improve the order and stability of the supramolecular mesophases, and enable tuneability of the optical and electronic properties, which can potentially be exploited for advanced applications in display technologies, photonic devices, sensors, and organic electronics. We recently successfully reported the straightforward synthesis of several mesogens containing four lateral aliphatic chains and derived from the classical triphenylene core self-assembling in columnar mesophases based on this paradigm. These mesogenic compounds were simply obtained in good yields by the nucleophilic substitution (SFAr) of various types of commercially available fluoroarenes with the electrophilic organolithium derivatives 2,2'-dilithio-4,4',5,5'-tetraalkoxy-1,1'-biphenyl (2Li- ).
Electrophilic aromatic substitution at the C5 position of isoxazolines and construction of a new quaternary carbon center were achieved in this paper. This is the first report of carbon-carbon (C-C) bond formation onto isoxazoline without compromising the ring structure. Various aromatics including heteroaromatics gave the desired products in good yields, especially aromatics bearing electron-donating groups.
Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa, 30 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
The integration of fluorine into medicinal compounds has become a widely used strategy to improve the biochemical and therapeutic properties of drugs. Inclusion of -CFH and -OCF fluoroalkyl groups has garnered attention due to their bioisosteric properties, enhanced lipophilicity, and potential hydrogen-bonding capability in bioactive substances. In this study, we prepared a series of stable Cu[CF(OCF)(CFH)]L complexes by insertion of commercially available perfluoro(methyl vinyl ether), CF=CF(OCF), into Cu-H bonds derived from Stryker's reagent, [CuH(PPh)], using ancillary ligands L.
We report copper(II) and copper(III) trifluoromethyl complexes supported by a pyridinedicarboxamide ligand (L) as a platform for investigating the role of electron transfer in C(sp)-H trifluoromethylation. While the copper(II) trifluoromethyl complex is unreactive towards (hetero)arenes, the formal copper(III) trifluoromethyl complex performs C(sp)-H trifluoromethylation of a wide range of (hetero)arenes. Mechanistic studies using the copper(III) trifluoromethyl complex suggest that the mechanism of arene trifluoromethylation is substrate-dependent.
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Catalytic asymmetric α-alkylation of simple carboxylic acid derivatives is a challenging issue due to the difficulties in achieving high catalytic efficiency and controlling the enantioselectivity. Herein, by using a copper(I)-()-DTBM-SEGPHOS complex as a catalyst and 2-acylimidazoles as pronucleophiles, a general method for the catalytic asymmetric α-alkylation of simple carboxylic acid derivatives is accomplished. Various alkyl electrophiles, including allyl bromides, benzyl bromides, propargyl bromide, and unactivated alkyl sulfonates, serve as efficient alkylation reagents.
