Browse
Submit Data
Databases
API
Help

Dataset Information

18 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Enhanced Synthetic Access to Tris-CF₃-Substituted Corroles.

ABSTRACT: Separate focus on the oligomerization and oxidative cyclization steps required for the synthesis of 5,10,15-tris(trifluoromethyl)corrole revealed [bis(trifluoroacetoxy)iodo]benzene (PIFA) as a superior alternative oxidant. Under optimized conditions, the pure free-base corrole was obtained with a 6-fold increase in chemical yield and an 11-fold rise in isolated material per synthesis. The corresponding gallium(III) and manganese(III) complexes were isolated by adding the appropriate metal salt prior to corrole purification.

SUBMITTER: Yadav P

PROVIDER: S-EPMC7187640 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Cross-dehydrogenative coupling enables enantioselective access to CF3-substituted all-carbon quaternary stereocenters.

Project description:A cross-dehydrogenative coupling strategy for enantioselective access to acyclic CF3-substituted all-carbon quaternary stereocenters has been established. By using catalytic DDQ with MnO2 as an inexpensive terminal oxidant, asymmetric cross coupling of racemic δ-CF3-substituted phenols with indoles proceeded smoothly, providing CF3-bearing all-carbon quaternary stereocenters with excellent chemo- and enantioselectivities. The generality of the strategy is further demonstrated by efficient construction of all-carbon quaternary stereocenters bearing other polyfluoroalkyl and perfluoroalkyl groups such as CF2Cl, C2F5, and C3F7.

| S-EPMC8157275 | biostudies-literature

Direct Access to Substituted 4-CF3 β-Lactams at the C-3 Position.

Project description:Mono- and disubstituted 4-CF3 β-lactams at the C-3 position have been obtained stereoselectively under basic conditions. A wide range of function such as alcohols, alkyls, aryls, esters, and double and triple bonds have been introduced.

| S-EPMC6691124 | biostudies-literature

Pd-Catalyzed Allylation of Imines to Access α-CF3-Substituted α-Amino Acid Derivatives.

Project description:We herein report a high yielding protocol for the direct α-allylation of easily accessible trifluoropyruvate-derived imines using Pd-catalysis. The reaction gives access to a variety of different α-allylated-α-CF3-amino acids in a straightforward manner, starting from commercially available trifluoropyruvate. We also provide a proof-of-concept for an enantioselective protocol (up to er = 75:25) by using chiral phosphane ligands.

| S-EPMC6887540 | biostudies-literature

Access to N-CF3 Formamides by Reduction of N-CF3 Carbamoyl Fluorides.

Project description:The departure into unknown chemical space is essential for the discovery of new properties and function. We herein report the first synthetic access to N-trifluoromethylated formamides. The method involves the reduction of bench-stable NCF3 carbamoyl fluorides and is characterized by operational simplicity and mildness, tolerating a broad range of functional groups as well as stereocenters. The newly made N-CF3 formamide motif proved to be highly robust and compatible with diverse chemical transformations, underscoring its potential as building block in complex functional molecules.

| S-EPMC10099374 | biostudies-literature

Photoinduced Trifluoromethylation with CF3Br as a Trifluoromethyl Source: Synthesis of α-CF3-Substituted Ketones.

Project description:An efficient and novel photoinduced trifluoromethylation employing CF3Br as a trifluoromethyl source is described. With commercially accessible fac-Ir(III)(ppy)3 as the catalyst, radical trifluoromethylation between O-silyl enol ether and CF3Br occurs successfully. This method provides various α-CF3-substituted ketones with a broad substrate scope in good yields under mild reaction conditions.

| S-EPMC9089747 | biostudies-literature

Iridium-Catalyzed C-H Borylation of CF3-Substituted Pyridines.

Project description:Iridium-catalyzed C-H borylation of CF3-substituted pyridines is described in this paper. The boronic ester group can be installed on the α, β, or γ position of pyridine by an appropriate substitution pattern. Sterically governed regioselectivity provides convenient access to a variety of CF3-substituted pyridylboronic esters. These catalytic C-H borylation reactions were carried out neatly without the use of any solvent. Several functional groups, such as halo, ester, alkoxy, amino, etc., are compatible with this methodology. These pyridylboronic esters are amenable to column chromatography and the products were isolated in good to excellent yields. α-Borylated pyridines, although isolated in good yields, do not have a long shelf life. The boronic ester derivatives of these CF3-substituted pyridines can serve as useful precursors in the synthesis regime.

| S-EPMC8992268 | biostudies-literature

Synthesis and characterization of meso-substituted A2B corroles with extended π-electronic structure.

Project description:AbstractWe report the chemical synthesis and characterization of the stable 5,15-bis(pentafluorophenyl)-10-(trimethylsilylethynyl)corrole which serves as a precursor for the subsequent in situ sila-Sonogashira-cross-coupling reaction and metalation with copper(II) acetate. Under ambient conditions and a common catalyst system the reaction with 1-iodopyrene occurred within five hours. Due to the direct conjugation of the 18π-electronic system of the corrole macrocycle over the alkynyl group to the pyrene moiety the optical transitions in the Soret (B-) band Q-band region are significantly altered. The copper corrole exhibited complex hyperfine and superhyperfine structure in the EPR spectrum. The assignment of the EPR spectrum reveals the existence of an axial [CuII-cor∙+] species.Graphical abstract

| S-EPMC5906495 | biostudies-literature

Formation of synthetically relevant CF3-substituted phenonium ions in superacid media.

Project description:Predestined to be transient theoretical species, phenonium ions can now be considered as cationic intermediates of choice in organic synthesis. Here, we demonstrate that under non-nucleophilic and superacidic conditions, CF3-substituted phenonium ions can be generated to furnish original CF3-substituted dihydrostilbenes of interest.

| S-EPMC9036966 | biostudies-literature

The [3+2] Annulation of CF3-Ketimines by Re Catalysis: Access to CF3-Containing Amino Heterocycles and Polyamides.

Project description:Transition metal catalyzed [3 + 2] annulation of imines with double bonds via directed C-H activation offers a direct access to amino cyclic motifs. However, owing to weak coordination and steric hindrance, trifluoromethylated ketimines have been an unaddressed challenge for TM-catalyzed annulations. Here, a rhenium-catalyzed [3 + 2] annulation of trifluoromethylated ketimines with isocyanates via C(sp2)-H activation has been disclosed. This approach provides an efficient platform for rapid access to a privileged library of CF3-containing iminoisoindolinones and polyamides by utilizing challenging CF3-ketimines as the annulation component. The capability of gram scale synthesis, the post-functionalization of the cyclization adduct, the derivation of complex natural molecules and the facile synthesis of polyamides highlight a diversity of synthetic potential of the current methodology.

| S-EPMC7644752 | biostudies-literature

Theoretical insight into OH- and Cl-initiated oxidation of CF3OCH(CF3)2 and CF3OCF2CF2H &fate of CF3OC(X•)(CF3)2 and CF3OCF2CF2X• radicals (X=O, O2).

Project description:In this study, the mechanistic and kinetic analysis for reactions of CF3OCH(CF3)2 and CF3OCF2CF2H with OH radicals and Cl atoms have been performed at the CCSD(T)//B3LYP/6-311++G(d,p) level. Kinetic isotope effects for reactions CF3OCH(CF3)2/CF3OCD(CF3)2 and CF3OCF2CF2H/CF3OCF2CF2D with OH and Cl were estimated so as to provide the theoretical estimation for future laboratory investigation. All rate constants, computed by canonical variational transition state theory (CVT) with the small-curvature tunneling correction (SCT), are in reasonable agreement with the limited experimental data. Standard enthalpies of formation for the species were also calculated. Atmospheric lifetime and global warming potentials (GWPs) of the reaction species were estimated, the large lifetimes and GWPs show that the environmental impact of them cannot be ignored. The organic nitrates can be produced by the further oxidation of CF3OC(•)(CF3)2 and CF3OCF2CF2• in the presence of O2 and NO. The subsequent decomposition pathways of CF3OC(O•)(CF3)2 and CF3OCF2CF2O• radicals were studied in detail. The derived Arrhenius expressions for the rate coefficients over 230-350?K are: k T(1)?=?5.00?×?10-24T3.57 exp(-849.73/T), k T(2)?=?1.79?×?10-24T4.84 exp(-4262.65/T), kT(3)?=?1.94?×?10-24 T4.18 exp(-884.26/T), and k T(4)?=?9.44?×?10-28T5.25 exp(-913.45/T) cm3 molecule-1 s-1.

| S-EPMC5220334 | biostudies-literature