This communication describes a mild, amide-directed fluorination of benzylic, allylic, and unactivated C-H bonds mediated by iron. Upon exposure to catalytic amount iron(II) triflate (Fe(OTf)2), N-fluoro-2-methylbenzamides undergo chemoselective fluorine transfer provide the corresponding fluorides in high yield. The reaction demonstrates broad substrate scope functional group tolerance without use any noble metal additives. Mechanistic computational experiments suggest that proceeds through...

The installation of trifluoromethyl groups has become an essential step across a number industries such as agrochemicals, drug discovery, and materials. Consequently, the rapid introduction this critical functional group in predictable fashion would benefit current practitioners those fields. This communication describes mild trifluoromethylation benzylic C–H bonds with high selectivity for least hindered hydrogen atom. reaction provides monotrifluoromethylation proceeds environmentally...

Electrospray ionization (ESI) combined with ion mobility spectrometry (IMS) and mass (MS) techniques is used to examine the Biginelli reaction in an ensemble of ions generated from droplets.

The direct, catalytic substitution of unactivated alcohols remains an undeveloped area organic synthesis. Moreover, activation this difficult electrophile with predictable stereo-outcomes presents even more formidable challenge. Described herein is a simple iron-based catalyst system which provides the mild, direct conversion secondary and tertiary to sulfonamides. Starting from enantioenriched alcohols, intramolecular variant proceeds stereoinversion produce 2- 2,2-subsituted pyrrolidines...

Abstract Modifying the electronic properties of olefins is quintessential approach to tuning alkene reactivity. In this context, exploration trifluoromethyl groups as divergent modifiers has not been considered. work, we describe a copper‐mediated 1,2‐(bis)trifluoromethylation acetylenes create E ‐hexafluorobutenes ( ‐HFBs) under blue light in single step. The reaction proceeds with high yield and / Z selectivity. Since alkyne captures two from each molecule bpyCu(CF 3 ) , mechanistic...

Site-selective fluorination of aliphatic C-H bonds remains synthetically challenging. While directed represents the most promising approach, limited work conducted to date has enabled just a few functional groups as arbiters direction. Leveraging insights gained from both computations and experimentation, we use ubiquitous amine group handle for Csp3-H bonds. By converting primary amines adamantoyl-based fluoroamides, site-selective proceeds under influence simple iron catalyst in 20...

An adj-dicarbaporphyrin was prepared by carrying out a base-catalyzed MacDonald reaction between bis(3-indenyl)methane and dipyrrylmethane dialdehyde. The porphyrinoid system exhibited highly diatropic characteristics, the proton NMR spectrum gave resonances at -5.74 -6.24 ppm for internal NH CH protons, respectively. UV-vis also porphyrin-like, giving Soret band 455 nm series of Q bands longer wavelengths. Addition trifluoroacetic acid C-protonated monocation, higher concentrations...

A series of porphyrinoids fused to highly electron-withdrawing bis(thiadiazolo)benzene units have been prepared and spectroscopically characterized. These structures modified chromophores exhibit large bathochromic shifts. The nickel(II), copper(II) zinc complexes a bis(thiadiazolo)benzoporphyrin were prepared, these showed strong absorptions above 600 nm that shifted longer wavelengths with increasing atomic number for the coordinated metal cations. Although investigated poorly soluble,...

Monocarbaporphyrins, dicarbaporphyrins, tricarbaporphyrins, and quatyrins can all potentially exist in a number of tautomeric forms, but little is known about these species. In addition, no examples tricarbaporphyrins or are at this time. order to get information on the relative stabilities carbaporphyrin tautomers, series aromatic nonaromatic structures were assessed using computational methods. The conformations 41 structures, together with four tautomers porphyrin related antiaromatic...

The first examples of porphyrin analogues incorporating pyrene units are reported. Acid-catalyzed condensation a dialdehyde with tripyrrane, followed by oxidation DDQ, afforded polycyclic aromatic hydrocarbon (PAH)-porphyrin hybrid in 38% yield. Pyreniporphyrin proved to be devoid global character, but upon protonation mono- and dicationic species were generated. In the proton NMR spectrum for dication, internal CH was shifted upfield approximately +3 ppm. NICS calculations ACID plots...

The conformations and relative stabilities of a series benziporphyrin naphthiporphyrin tautomers were calculated the diatropic properties each these species assessed. results in good agreement with experimental observations allow favorable delocalization pathways to be identified.

In an attempt to prepare quatyrin derivatives, which are hydrocarbon analogues of the porphyrins, azulene-appended fulvene carbinols were self-condensed in presence BF3·Et2O. Although these investigations failed give structures related quatyrin, expanded porphyrin obtained instead. dichloromethane, major macrocyclic product consisted three units, but when chloroform was used as reaction solvent, a tetrafulvene macrocycle isolated. Self-condensation furan-appended alcohol gave trace amounts...

The conformations of eight neo-confused porphyrin (neo-CP) structures and seven related benzo-neo-confused porphyrins (B-neo-CPs) were minimized using DFT-B3LYP/6-311++G(d,p). In addition, in order to provide contrasts the B-neo-CP tautomers, a series twelve benzoporphyrin (BP) tautomers benzocarbaporphyrins (BCPs) also analyzed, two N-confused (NCP) considered. relative stability for each was computed, bond lengths angles calculated. Surprisingly, all neo-CP near planar. fully conjugated...

Base-catalyzed condensation of dicyclopentadienylmethane with a dipyrrylmethane dialdehyde gave dicarbachlorin an internal CH₂ group.

Previous attempts to prepare tropone-fused carbaporphyrins by reacting peroxides with azuliporphyrins under basic conditions afforded benzocarbaporphyrins instead. In this study, a methoxyazulitripyrrane condensed pyrrole dialdehyde in the presence of TFA, followed oxidation ferric chloride, give carbaporphyrin following spontaneous demethylation. The porphyrinoid gave modified UV–vis spectrum showing multiple bands Soret region, and proton NMR showed that it has reduced diamagnetic ring...

Acid-catalyzed condensation of a benzo[f]indane dialdehyde with tripyrrane, followed by an oxidation step, afforded the first example naphtho[2,3-b]-21-carbaporphyrin. This π-extended porphyrinoid system is strongly aromatic and gave porphyrin-like UV–vis spectrum Soret band at 432 nm. Protonation TFA monocation, but under highly acidic conditions C-protonated dication was generated. Reaction naphthoporphyrin ferric chloride produced 21-chloro derivative. Alkylation methyl iodide potassium...

Oxidation of tetraarylazuliporphyrins with silver(I) acetate in refluxing chloroform-acetonitrile afforded good yields 21-oxyazuliporphyrins. Although hydroxyazuliporphyrin tautomers can be considered for this system, spectroscopic results and density functional theory calculations indicate that the keto form is favored, was confirmed by single-crystal X-ray diffraction. Oxyazuliporphyrins formally possess a 24π electron delocalization pathway, but proton NMR spectra are consistent...

The reaction of a carbatripyrrin with tellurophene dicarbinol in the presence BF3·Et2O, followed by oxidation DDQ, afforded first example telluracarbaporphyrin. Although this system exhibits strongly aromatic characteristics, it is prone to air oxidation, giving rise hydroxy derivative that was characterized X-ray crystallography. initial telluracarbaporphyrin reacted palladium(II) acetate give stable organometallic complex, and crystallography showed palladium cation coordinated all four...

Connectivity-Based Hierarchy (CBH) is an effective error-cancellation scheme for the determination of chemically accurate thermochemical properties a variety organic and biomolecules. Neutral molecules open-shell radicals have already been treated successfully by this approach utilizing inexpensive computational methods such as density functional theory. Herein, we present extension method to new class molecules, specifically, cations. Because presence structural rearrangements involving...

The conformations of five doubly neo-confused porphyrin structures and fifty-four N-confused (neo-C-NCP) tautomers were minimized using DFT-B3LYP/6-311++G(d,p). relative stabilities the for each series computed M06-2X B3LYP-D functionals, bond lengths angles calculated. Nucleus-independent chemical shifts anisotropy induced current density plots used to provide further insights into diatropic properties species. results demonstrate that porphyrinoid with two modified rings this type are far...

DFT studies have been carried out on 46 azuliporphyrin (AzP) and tropiporphyrin (TrP) tautomers, cations, dications. The structures were minimized using DFT-B3LYP/6-311++G(d,p), the relative stabilities of tautomers for each series computed with M06-2X B3LYP-D3 functionals. Nucleus independent chemical shifts, both NICS(0) NICS(1) zz, calculated center macrocycles individual pyrrolic carbocyclic subunits. In addition, anisotropy induced current density (AICD) plots generated all species...

A series of diformylbenzophenones were generated by sequentially reacting protected bromobenzaldehydes with n-butyllithium and ethyl N,N-dimethylcarbamate. The acetal protective groups cleaved refluxing formic acid. Vilsmeier-Haack formylation 2,2',4,4'-tetramethoxybenzophenone also afforded a related dialdehyde. MacDonald "2 + 2" condensation three benzophenone dialdehydes dipyrrylmethane gave oxophlorin analogues constructed from two benzene pyrrole rings. free base oxodibenziphlorins...

Bis(pyrrolylmethyl)azulene dialdehydes underwent intramolecular McMurry coupling, and following oxidation with DDQ addition of trifluoroacetic acid, gave aromatic azulitriphyrin cations. The proton NMR spectra for these contracted carbaporphyrinoids showed the internal CH upfield at ca. 2 ppm, while bridging methine units appeared downfield between 8 10 demonstrating that macrocycles possess significant 14π electron diamagnetic ring currents. Although protonated azulitriphyrins(1.2.1) proved...

Isocitrate dehydrogenase 1 (IDH1) mutations that generate the oncometabolite 2‐hydroxyglutarate (2‐HG) from α‐ketoglutarate (α‐KG) have been identified in many types of tumors and are an important prognostic factor gliomas. 2‐HG production can be determined by hyperpolarized carbon‐13 magnetic resonance spectroscopy (HP‐ 13 C‐MRS) using [1‐ C]‐α‐KG as a probe, but peak contamination naturally occurring [5‐ overlaps with C]‐2‐HG peak. Via newly developed oxidative‐Stetter reaction, C‐5‐ 12...

Reaction of 6-nitrochrysene with ethyl isocyanoacetate in the presence a non-nucleophilic base gave c-annulated pyrrole ester that was used to prepare chrysene-fused tripyrranes and chrysopyrrole dialdehyde. Chrysene-fused were reacted dialdehyde, but poor yields chrysoporphyrins obtained. However, condensation dialdehyde series afforded excellent an acenaphtho-chrysoporphyrin. Iron(III) chloride mediated oxidative cyclization dihexylchrysoporphyrin benzopyrene-fused porphyrin exhibited...